CN107629202A - A kind of poly- polysaccharide of ring improves the hydrophilic method of PPDO and application - Google Patents
A kind of poly- polysaccharide of ring improves the hydrophilic method of PPDO and application Download PDFInfo
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Abstract
A kind of poly- polysaccharide of ring improves the hydrophilic method of PPDO, including：PPDO solid powder is added in the poly- polysaccharide solution of ring, at 30~50 DEG C after 36~120h of stirring reaction, reactant solution is precipitated, separated, is washed, is dried, ring is obtained and gathers polysaccharide-modified PPDO.Above-mentioned product is placed in 0.02~2mm of thickness, in 5~20mm of radius circle hole shape mould, 3~5min is preheated on hot press, pressure is 5~15min of hot pressing under 5~10Mpa, cold-press bed cooling shaping is transferred to, ring is obtained and gathers polysaccharide-modified PPDO thin slice.The present invention is simple to operate, is easy to grasp, reproducible, and product is easily isolated purification, and the hydrophily that gained is modified PPDO is had clear improvement, and 13~38 ° are reduced before modified with the surface contact angle ratio of water.
Description
Technical field
The present invention relates to one kind to improve the hydrophilic method of PPDO and application, belongs to high polymer material function
Change technical field.
Background technology
PPDO (PPDO) is a kind of excellent biodegradation material, has excellent tensile strength, flexible
Property and knot strength, be food and medicine Surveillance Authority of the U.S. approval the first monofilament suture materials, be widely used in
The health fields such as orthopaedics tissue engineering bracket, drug delivery, blood vessel braiding.PPDO glass transition temperature is about -10 DEG C, is a kind of
Semicrystalline polymeric, stronger hydrophobicity weaken its compatibility with soft biological tissue and hydrophilic biological macromolecule,
Also so that its degradation behavior has discontinuity, limit it and widely applied in biomedical materials field.Therefore PPDO materials
It is always study hotspot in recent years to expect hydrophilic study on the modification.
It is to improve one of hydrophilic common methods of PPDO by the polymer containing hydrophilic radical and PPDO blendings.Zheng
Deng (Li Z, Yuzhong W, Keke Y, et al, European Polymer Journal, 2005,41：1243-1250.) first
Secondary polyethylene glycol (PEG) and the PPDO of employing carries out blending and modifying, crystallinity, grain density and the hydrophily of material have compared with
Big degree improves.Zhou etc. (Zhou Z X, Wang X L, Wang Y Z, et al, Polymer International,
2006,55 (4)：383-390.) it is modified using polyvinyl alcohol (PVA) and PPDO blendings, PVA addition causes the heat of material
Stability and water solubility are all significantly improved.(Wang X L, Yang K K, Wang Y Z, the et al, Acta such as Wang
Materialia, 2004,52 (16)：4899-4905.) starch containing a large amount of hydrophilic radicals and PPDO are blended, what is obtained is total to
The crystallinity and hydrophily of mixed material are all significantly increased.But blending improves the hydrophilic methods of PPDO and still suffers from some shortcomings.
The problem of otherness and compatibility of unitary space structure is blended causes modifying process to become more to complicate.It is compatible to obtain
Property good co-mixing system, also need to modify blending unit skeleton sometimes and then improve the similitude of both structures.
One of common method that copolymerization and PPDO are modified.PEG and PPDO is copolymerized to obtain PPDO-b-PEG-b-PPDO tri- embedding
Section copolymer, as water soluble molecules segment PEG increase, the water imbibition of material accordingly increase in block copolymer, and
Dispersiveness of the nano-particle prepared by block copolymerization in water is very good.PPDO and polyhydroxy substance such as polyvinyl alcohol, shell
The graft copolymer of the formation such as poly- sugar and starch can be obviously improved its PPDO hydrophily.But PPDO is improved using copolymerization process
There is also shortcomings for hydrophilic mode：Severe reaction conditions, polymerization process controllability is not strong, accessory substance it is more and separation compared with
The deficiencies of cumbersome, make it that this method is not complex easy to operate.
The poly- polysaccharide molecule cyclodextrin of ring is a kind of nontoxic and has excellent biodegradability and carbohydrate physiologically active
Biological substance, has an axisymmetric frustroconical structure, and molecular structure is cylindrical.In the portlet of frustroconical structure
It is made up of 7 primary hydroxyls on C-6 positions, large port is made up of 14 secondary hydroxyls on C-2 and C-3 positions；Hydroxyl is gathered in molecule
Outer ledge, therefore molecule outer wall has stronger hydrophily；Inner chamber is by the hydrogen atom on C-3 and C-5 positions and C-4 positions
Oxygen atom forms；Hydrogen atom on C-3 and C-5 positions has its inner chamber to having shielding action with glycosyloxy atom on C-4 positions
Stronger hydrophobicity.Therefore cyclodextrin be able to can be identified with reference to various substrates by non-covalent interaction.Pasted using ring
This characteristic of essence, using cyclo-dextrin-modified PPDO, can be formed relatively steady by caused intermolecular interaction between the two
Fixed structure.
Cyclodextrin molecular internal cavity is not still actually empty in a solvent either in solid phase, but is combined with water
Molecule.The tension force that cavity bound water molecule has, it is released when PPDO macromolecular chains enter cavity, and PPDO macromolecular chains
Cyclodextrin molecular cavity can be entered, remain stable by means of Van der Waals force, hydrogen bond, dipolar interaction, while itself still retains one
Fixed movement and rotary freedom, and with the volume of PPDO macromolecular chains, geometry and in the poly- polysaccharide molecule cavity of ring
The tightness degree of filling is relevant.Substituted the hydrone discharged to be condensed into liquid by " gaseous state " by PPDO, cause the change of entropy, enthalpy
To change, the moisture subdivision of release compensate for the Entropy Changes caused by cyclodextrin molecular is combined with PPDO macromolecular chains, and final two
Person forms metastable structure, is improved so as to PPDO hydrophily.
The content of the invention
The present invention is directed to the defects of PPDO hydrophilies are poor, and open one kind improves PPDO using the poly- polysaccharide of ring
Hydrophilic method.The present invention is simple to operate, is easy to grasp, reproducible, and product is easily isolated purification, and gained is modified poly- to two
The hydrophily of oxygen cyclohexanone has clear improvement.
Technical scheme：
A kind of poly- polysaccharide of ring improves PPDO (PPDO) hydrophilic method, and this method is in PPDO macromoleculars
Chain periphery parcel the poly- polysaccharide of ring containing hydrophilic radical, obtain ring and gather polysaccharide-modified PPDO, with increase PPDO with
The engagement capacity of hydrone.Its method of modifying uses following steps：
1. ring gathers the synthesis of polysaccharide-modified PPDO：PPDO solid powder is added into ring to gather
In polysaccharide solution, at 30~50 DEG C after 36~120h of stirring reaction, resulting solution is added dropwise to dropwise in excessive precipitating reagent and sunk
Form sediment, be then centrifuged for isolated sediment, it is washed under suction filtration state using multi-solvents, is then dried in vacuo 12
~36h, repeated washing and drying process 2~3 times, obtain ring and gather polysaccharide-modified PPDO.
Described PPDO viscosity average molecular weigh scope is Mη=(1.0~3.0) × 105G/mol, its solution are dense
Spend for 0.5~2.5g/100mL；The poly- polysaccharide of ring is alpha-cyclodextrin, beta-schardinger dextrin or gamma-cyclodextrin etc., and the solvent of its solution can be with
For DMF, hexafluoroisopropanol or dimethyl sulfoxide (DMSO) etc., solution concentration is 0.03~5.0g/100mL；Described
Precipitation process precipitation solvent can be ether or ethanol；Reactant solution is 1 with precipitating reagent volume ratio:2~3；It is described washed
Cleaning solvent can be DMF, hexafluoroisopropanol, dimethyl sulfoxide (DMSO), 1 in journey, 1,2,2- tetrachloroethanes or go
Ionized water etc..
2. ring gathers the application of polysaccharide-modified PPDO, gather polysaccharide-modified PPDO thin slice for ring
Preparation：Ring dried in above-mentioned 1 is gathered into polysaccharide-modified PPDO and is placed in 0.02~2mm of thickness, radius 5~
In 20mm circle hole shape mould, 3~5min is preheated on hot press, pressure is 5~15min of hot pressing under 5~10Mpa, is transferred to
Cold-press bed cooling shaping, obtains ring and gathers polysaccharide-modified PPDO thin slice, carry out water contact angle test.
The present invention compared with the prior art for, its advantage is：
The poly- polysaccharide molecule cyclodextrin of ring improves the hydrophilic methods of PPDO, simpler, efficiently, product asepsis environment-protecting, area
The mode occurred not in standard copolymerization modifying process with a variety of chemical reactions, the generation of no coupling product of the present invention, and target
Product is easily isolated purification.
Embodiment
Embodiment 1
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is alpha-cyclodextrin, and step is as follows：
1. 0.015g alpha-cyclodextrins are dissolved into 40mL hexafluoroisopropanols, stirring and dissolving at 30 DEG C.
2. by 0.3g Mη=1.09 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 30 DEG C
React 36h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 120mL ethanol dropwise, stirring is precipitated.Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, hexafluoroisopropanol washes twice.Sediment after washing is placed in drying at room temperature 12h in vacuum drying chamber, and repeats above-mentioned wash
Wash drying process 2 times, obtain target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.08mm,
In radius 10mm circle hole shape mould, 3min is preheated on hot press, pressure is hot pressing 5min under 5Mpa, is transferred to cold-press bed drop
Temperature shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 13.5 ° before modified.
Embodiment 2
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is alpha-cyclodextrin, and step is as follows：
1. 0.03g alpha-cyclodextrins are dissolved into 60mLN, in dinethylformamide, stirring and dissolving at 50 DEG C.
2. by 0.3g Mη=1.09 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 50 DEG C
React 96h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 180mL ether dropwise, stirring is precipitated；Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
It is secondary, 1,1,2,2 ,-tetrachloroethanes washes twice.Sediment after washing is placed in drying at room temperature 24h in vacuum drying chamber, and repeated
Above-mentioned washing drying process 2 times, obtains target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 1mm, radius
In 5mm circle hole shape mould, preheat 5min on hot press, pressure is hot pressing 10min under 8Mpa, be transferred to cold-press bed cooling into
Type, obtain ring and gather polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 25 ° before modified.
Embodiment 3
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is alpha-cyclodextrin, and step is as follows：
1. 2.5g alpha-cyclodextrins are dissolved into 50mL dimethyl sulfoxide (DMSO)s, stirring and dissolving at 40 DEG C.
2. by 1.25g Mη=2.12 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 40 DEG C
React 96h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 150mL ether dropwise, stirring is precipitated；Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, dimethyl sulfoxide (DMSO) washes twice.Sediment after washing is placed in drying at room temperature 36h in vacuum drying chamber, and repeats above-mentioned wash
Wash drying process 2 times, obtain target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.08mm,
In radius 15mm circle hole shape mould, 4min is preheated on hot press, pressure is hot pressing 15min under 8Mpa, is transferred to cold-press bed
Cooling shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 32 ° before modified.
Embodiment 4
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is alpha-cyclodextrin, and step is as follows：
1. 0.9g alpha-cyclodextrins are dissolved into 60mL hexafluoroisopropanols, stirring and dissolving at 50 DEG C.
2. by 0.9g Mη=2.12 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 50 DEG C
React 120h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 150mL ethanol dropwise, stirring is precipitated；Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, hexafluoroisopropanol washes twice.Sediment after washing is placed in drying at room temperature 36h in vacuum drying chamber, and repeats above-mentioned wash
Wash drying process 3 times, obtain target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.08mm,
In radius 20mm circle hole shape mould, 5min is preheated on hot press, pressure is hot pressing 15min under 10Mpa, is transferred to cold-press bed
Cooling shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 31 ° before modified.
Embodiment 5
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is beta-schardinger dextrin, and step is as follows：
1. 0.015g beta-schardinger dextrins are dissolved into 40mL hexafluoroisopropanols, stirring and dissolving at 30 DEG C.
2. by 0.3g Mη=1.09 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 30 DEG C
React 72h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 120mL ethanol dropwise, stirring is precipitated；Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is washed through deionized water (quick) respectively under the conditions of suction filtration
Wash twice, hexafluoroisopropanol washes twice.Sediment after washing is placed in drying at room temperature 24h in vacuum drying chamber, and repeated
Above-mentioned washing drying process 2 times, obtains target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.02mm,
In radius 20mm circle hole shape mould, 3min is preheated on hot press, pressure is hot pressing 10min under 10Mpa, is transferred to cold-press bed
Cooling shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 15.5 ° before modified.
Embodiment 6
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is beta-schardinger dextrin, and step is as follows：
1. 0.96g beta-schardinger dextrins are dissolved into 60mLN, in dinethylformamide, stirring and dissolving at 50 DEG C.
2. by 0.6g Mη=1.09 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 50 DEG C
React 120h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 180mL ether dropwise, stirring is precipitated；Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, DMF washes twice.Sediment after washing is placed in drying at room temperature 36h in vacuum drying chamber, laid equal stress on
Multiple above-mentioned washing drying process 2 times, obtains target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 1mm, radius
In 10mm circle hole shape mould, 3min is preheated on hot press, pressure is hot pressing 15min under 10Mpa, is transferred to cold-press bed cooling
Shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 35 ° before modified.
Embodiment 7
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is beta-schardinger dextrin, and step is as follows：
1. 0.06g beta-schardinger dextrins are dissolved into 40mL dimethyl sulfoxide (DMSO)s, stirring and dissolving at 40 DEG C.
2. by 0.6g Mη=2.12 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 40 DEG C
React 120h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 120mL ethanol dropwise, stirring is precipitated；Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, dimethyl sulfoxide (DMSO) washes twice.Sediment after washing is placed in drying at room temperature 24h in vacuum drying chamber, and repeated above-mentioned
Wash drying process 3 times, obtain target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.08mm,
In radius 20mm circle hole shape mould, 5min is preheated on hot press, pressure is hot pressing 15min under 10Mpa, is transferred to cold-press bed
Cooling shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 24 ° before modified.
Embodiment 8
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is beta-schardinger dextrin, and step is as follows：
1. 0.24g beta-schardinger dextrins are dissolved into 50mLN, in dinethylformamide, stirring and dissolving at 50 DEG C.
2. by 0.3g Mη=2.12 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 50 DEG C
React 72h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 100mL ether dropwise, stirring is precipitated；Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, DMF washes twice.Sediment after washing is placed in drying at room temperature 36h in vacuum drying chamber, laid equal stress on
Multiple above-mentioned washing drying process 2 times, obtains target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.02mm,
In radius 20mm circle hole shape mould, 3min is preheated on hot press, pressure is hot pressing 10min under 10Mpa, is transferred to cold-press bed
Cooling shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 38 ° before modified.
Embodiment 9
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is gamma-cyclodextrin, and step is as follows：
1. 0.045g gamma-cyclodextrins are dissolved into 40mL hexafluoroisopropanols, stirring and dissolving at 40 DEG C.
2. by 0.3g Mη=1.09 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 40 DEG C
React 72h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 80mL ethanol dropwise, stirring is precipitated；By gained precipitate with
10000r/min rotating speed centrifugation.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, hexafluoroisopropanol washes twice.Sediment after washing is placed in drying at room temperature 24h in vacuum drying chamber, and repeated above-mentioned
Wash drying process 3 times, obtain target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.2mm, half
In footpath 6mm circle hole shape mould, 3min is preheated on hot press, pressure is hot pressing 5min under 5Mpa, is transferred to cold-press bed cooling
Shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 27 ° before modified.
Embodiment 10
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is gamma-cyclodextrin, and step is as follows：
1. 0.03g gamma-cyclodextrins are dissolved into 60mLN, in dinethylformamide, stirring and dissolving at 50 DEG C.
2. by 0.3g Mη=1.09 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 50 DEG C
React 72h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 150mL ether dropwise, stirring is precipitated；Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, DMF washes twice.Sediment after washing is placed in drying at room temperature 36h in vacuum drying chamber, and repeated
Above-mentioned washing drying process 2 times, obtains target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.2mm, half
In footpath 6mm circle hole shape mould, 3min is preheated on hot press, pressure is hot pressing 10min under 10Mpa, is transferred to cold-press bed drop
Temperature shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 24.5 ° before modified.
Embodiment 11
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is gamma-cyclodextrin, and step is as follows：
1. 0.12g gamma-cyclodextrins are dissolved into 40mL dimethyl sulfoxide (DMSO)s, stirring and dissolving at 50 DEG C.
2. by 0.6g Mη=2.12 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 50 DEG C
React 120h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 120mL ether dropwise, stirring is precipitated；Gained is precipitated
Centrifuged with 10000r/min rotating speed.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, dimethyl sulfoxide (DMSO) washes twice.Sediment after washing is placed in drying at room temperature 24h in vacuum drying chamber, and repeats above-mentioned wash
Wash drying process 3 times, obtain target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.5mm, half
In footpath 10mm circle hole shape mould, 3min is preheated on hot press, pressure is hot pressing 10min under 10Mpa, is transferred to cold-press bed drop
Temperature shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 33 ° before modified.
Embodiment 12
1) ring gathers polysaccharide-modified PPDO synthesis, and the poly- polysaccharide molecule of ring is gamma-cyclodextrin, and step is as follows：
1. 0.36g gamma-cyclodextrins are dissolved into 30mL hexafluoroisopropanols, stirring and dissolving at 50 DEG C.
2. by 0.3g Mη=2.12 × 105G/mol PPDO is added in above-mentioned solution, and the magnetic agitation at 50 DEG C
React 36h.
After 3. reaction terminates, above-mentioned solution is added drop-wise in 90mL ethanol dropwise, stirring is precipitated；By gained precipitate with
10000r/min rotating speed centrifugation.Centrifugation gained precipitated product is under the conditions of suction filtration respectively through (quick) washing two of deionized water
Secondary, hexafluoroisopropanol washes twice.Sediment after washing is placed in drying at room temperature 36h in vacuum drying chamber, and repeats above-mentioned wash
Wash drying process 2 times, obtain target product.
2) ring gathers polysaccharide-modified PPDO preparations of sections：Above-mentioned 1) dried target product is placed in thickness 0.08mm,
In radius 20mm circle hole shape mould, 5min is preheated on hot press, pressure is hot pressing 10min under 10Mpa, is transferred to cold-press bed
Cooling shaping, obtains ring and gathers polysaccharide-modified PPDO thin slices.
After tested：The surface contact angle ratio of the present embodiment PPDO thin slices and water reduces 35.5 ° before modified.
Claims (6)
1. a kind of poly- polysaccharide of ring improves the hydrophilic method of PPDO, it is characterised in that：This method is to two poly-
Ring poly- polysaccharide of the oxygen cyclohexanone macromolecular chain periphery parcel containing hydrophilic radical, obtain ring and gather polysaccharide-modified gather to dioxocyclohex
Ketone, to increase the engagement capacity of PPDO and hydrone；The method of modifying uses following steps：
PPDO solid powder is added in the poly- polysaccharide solution of ring, at 30~50 DEG C stirring reaction 36~
120h, after reaction terminating, reactant solution is instilled in excessive precipitating reagent dropwise and precipitated, centrifuged, use two kinds or two kinds
After above different solvents wash in two steps, 12~36h, repeated washing and drying process 2~3 times are dried in vacuo, it is poly- more to obtain ring
The modified PPDO of sugar.
2. the poly- polysaccharide of a kind of ring according to claim 1 improves the hydrophilic method of PPDO, its feature exists
In：The PPDO viscosity average molecular weigh scope used is Mη=(1.0~3.0) × 105G/mol, PPDO
Solution concentration is 0.5~2.5g/100mL.
3. the poly- polysaccharide of a kind of ring according to claim 1 improves the hydrophilic method of PPDO, its feature exists
In：The poly- polysaccharide of ring is alpha-cyclodextrin, beta-schardinger dextrin or gamma-cyclodextrin, and the solvent in the poly- polysaccharide solution of ring is N, N- diformazans
Base formamide, hexafluoroisopropanol or dimethyl sulfoxide (DMSO), solution concentration are 0.03~5.0g/100mL.
4. the poly- polysaccharide of a kind of ring according to claim 1 improves the hydrophilic method of PPDO, its feature exists
In：The precipitating reagent of the precipitation process is ether or ethanol；The reactant solution is 1 with precipitating reagent volume ratio:2~3.
5. the poly- polysaccharide of a kind of ring according to claim 1 improves the hydrophilic method of PPDO, its feature exists
In：Cleaning solvent in the washing process is DMF, hexafluoroisopropanol, dimethyl sulfoxide (DMSO), 1,1,2,2-
Tetrachloroethanes or deionized water.
6. ring prepared by claim 1 methods described gathers the application of polysaccharide-modified PPDO, change for the poly- polysaccharide of ring
Property PPDO preparation of sections：Preparation process is as follows：
Ring dried in claim 1 is gathered into polysaccharide-modified PPDO and is placed in 0.02~2mm of thickness, radius 5~
In 20mm circle hole shape mould, 3~5min is preheated on hot press, pressure is 5~15min of hot pressing under 5~10Mpa, is transferred to
Cold-press bed cooling shaping, obtains ring and gathers polysaccharide-modified PPDO thin slice.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102552946A (en) * | 2012-03-01 | 2012-07-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Double-mode imaging and medicine-loading integrated nano medicine carrier and preparation method thereof |
| CN104861088A (en) * | 2015-06-04 | 2015-08-26 | 天津德奥赛恩生物科技有限公司 | Aliphatic polyester-cyclodextrin poly (pseudo) rotaxane and preparation method thereof |
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2017
- 2017-09-01 CN CN201710776780.2A patent/CN107629202A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102552946A (en) * | 2012-03-01 | 2012-07-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Double-mode imaging and medicine-loading integrated nano medicine carrier and preparation method thereof |
| CN104861088A (en) * | 2015-06-04 | 2015-08-26 | 天津德奥赛恩生物科技有限公司 | Aliphatic polyester-cyclodextrin poly (pseudo) rotaxane and preparation method thereof |
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| LIYUAN LI ET AL.: "Formation and characterization of pseudo-polyrotaxanes based on poly(p-dioxanone) and cyclodextrins", 《CARBOHYDRATE POLYMERS》 * |
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