CN107501531A - A kind of double block stabilizer HMTS PCL synthetic method - Google Patents
A kind of double block stabilizer HMTS PCL synthetic method Download PDFInfo
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- CN107501531A CN107501531A CN201710729263.XA CN201710729263A CN107501531A CN 107501531 A CN107501531 A CN 107501531A CN 201710729263 A CN201710729263 A CN 201710729263A CN 107501531 A CN107501531 A CN 107501531A
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- heptamethyltrisiloxane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
- C07F7/0879—Hydrosilylation reactions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The present invention relates to technical field prepared by biological medical degradable high polymer material, specifically a kind of synthetic method for being used for polyphosphazene polymer in supercritical fluid and sharing double block stabilizer HMTS PCL.The present invention under Speier catalyst actions, carries out Si―H addition reaction, generation hydroxypropyl heptamethyltrisiloxane HPHMTS using the active hydrogen and allyl alcohol of heptamethyltrisiloxane；Under the catalysis of stannous octoate, trigger caprolactone ring-opening polymerisation using the hydroxyl on HPHMTS, synthesize double block stabilizer HMTS PCL.The synthetic method of the present invention is simple, and reaction condition is gentleer, and the reaction time is short, and the product of synthesis can be used as double block stabilizers that biological medicine material polymerize in supercritical fluid, the dispersin polymerization available for bio-medical material in supercritical fluid.
Description
Technical field
It is specifically a kind of for overcritical the present invention relates to technical field prepared by biological medical degradable high polymer material
Polyphosphazene polymer shares double block stabilizer HMTS-PCL synthetic method in fluid.
Background technology
Supercritical carbon dioxide (ScCO2) technology is as the heat subject of numerous scholar's research, because it has source
Extensively, there are the diffusivity of similar gas and the density of liquid, nontoxic, inertia, the easily separated purifying of reaction product, make its work
For a kind of green solvent instead of many poisonous and hazardous organic solvents and is widely studied and applied, especially scattered poly-
Conjunction field is also able to promote and use.
Supercritical carbon dioxide can dissolve the nonpolar molecule and some polar molecules of most of low molecule amounts, but most of
Industrial widely used polymer can not be but dissolved under the conditions of relatively mild, only unformed fluoropolymer and silicon
Oxygen alkane polymer can be completely dissolved in supercritical carbon dioxide, and therefore, most of polymerisations in supercritical carbon dioxide are
It is heterogeneous, i.e. precipitation polymerization.There are some shortcomings in precipitation polymerization, as conversion ratio is low, molecular weight of product is smaller and product shape
State is irregular etc.., can be in polymer in the presence of stabilizer and dispersin polymerization can be largely overcoming these shortcomings
Certain active force with the formation of solvent interface, steric effect is produced by physical absorption or chemical graft to prevent the solidifying of particle
Poly-, dispersin polymerization can improve reaction efficiency and yield.The effect of dispersin polymerization is largely dependent on the effect of dispersion stabilizer
Effect.The synthetic method of stabilizer is studied, is had great importance for dispersin polymerization.
The content of the invention
It is stable with double blocks it is an object of the invention to provide bioabsorbable polymer material dispersin polymerization in a kind of supercritical fluid
Agent HMTS-PCL synthetic method.
For achieving the above object, technical scheme is as follows：
A kind of double block stabilizer HMTS-PCL synthetic method, using heptamethyltrisiloxane (HMTS) active hydrogen with
Allyl alcohol carries out Si―H addition reaction, generation hydroxypropyl heptamethyltrisiloxane (HPHMTS) under Speier catalyst actions；Pungent
Under the catalysis of sour stannous, trigger caprolactone (CL) ring-opening polymerisation using the hydroxyl on HPHMTS, synthesize double first of block stabilizer seven
Base trisiloxanes and polycaprolactone (HMTS-PCL)；Synthesis mechanism is as follows：
。
It the described method comprises the following steps：
(1) add allyl alcohol into reaction flask under nitrogen protection and dry the tetrahydrofuran (THF) of water removal, Ran Houjia
Enter Speier catalyst, after stirring, 4~6s/d is slowly dropped into the heptamethyltrisiloxane diluted by tetrahydrofuran, 20
DEG C~30 DEG C at, be stirred at reflux reaction 3~5 hours；Wherein the mol ratio of allyl alcohol and heptamethyltrisiloxane is 1:1~2, seven
The mass ratio of methyl trisiloxanes and Speier catalyst is 100~150:1；
(2) after the reaction of step (1) terminates, rotate, remaining solution is separated with chromatographic column after revolving, and petroleum ether is done
Eluant, eluent, after collecting cut revolving removing solvent, obtain hydroxypropyl heptamethyltrisiloxane colourless oil liquid；
(3) hydroxypropyl heptamethyltrisiloxane and caprolactone are added into flask, adds toluene under nitrogen protection to burning
In bottle, stannous octoate catalyst is then added, is heated to 100 DEG C~120 DEG C, 16~48 hours reaction time；Wherein hydroxypropyl
The mass ratio of heptamethyltrisiloxane and caprolactone is 1:1~2, the mass ratio of hydroxypropyl heptamethyltrisiloxane and stannous octoate
For 80~100:1；
(4) after the reaction of step (3) terminates, normal temperature is cooled to, is added methylene chloride after dissolving product, is slowly dropped into and is more than
In the refrigerated methanol (0~5 DEG C) of its 10 times of volumes, obtain white solid product, continue after filtering with a small amount of dichloromethane dissolve,
Precipitated in refrigerated methanol, repeatedly for three times, finally, product is placed in vacuum drying chamber and dried, obtain double block stabilizer HMTS-
PCL white solids.
The mol ratio of allyl alcohol and heptamethyltrisiloxane is 1 in above-mentioned steps (1):1.2, heptamethyltrisiloxane with
The mass ratio of Speier catalyst is 117:1,30 DEG C of reaction temperature, it is stirred at reflux the reaction time 4 hours.
The mass ratio of HPHMTS and caprolactone is 1 in above-mentioned steps (3):1.2, HPHMTS with the matter of octoate catalyst stannous
Amount is than being 90:1, heating-up temperature is 110 DEG C, and the reaction time is 24 hours.
Compared with prior art, the advantage of the invention is that：The active hydrogen and allyl of heptamethyltrisiloxane are used first
Alcohol carries out hydrosilylation under Speier catalyst actions, generates hydroxypropyl heptamethyltrisiloxane；In stannous octoate
Under catalysis, trigger caprolactone ring-opening polymerisation using the hydroxyl on hydroxypropyl heptamethyltrisiloxane, synthesize double block stabilizers
HMTS-PCL.The synthetic method of the present invention is simple, and reaction condition is gentleer, and the reaction time is short, and the product of synthesis can be used as surpassing
In critical fluids biological medicine material polymerize double block stabilizers, available in supercritical fluid bio-medical material disperse
Polymerization.
Brief description of the drawings
The infrared spectrogram of Fig. 1 heptamethyltrisiloxanes (HMTS) and hydroxypropyl heptamethyltrisiloxane (HPHMTS)；
The double block stabilizer HMTS-PCL proton nmr spectras of Fig. 2.
Embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
(1) Si―H addition reaction synthesis hydroxypropyl heptamethyltrisiloxane (HPHMTS)
1.9g allyl alcohol is added into three mouthfuls of reaction flasks under nitrogen protection and dries the 20mL tetrahydrofurans of water removal
(THF) the Speier catalyst (0.5mol/L chloroplatinic acids/aqueous isopropanol) of 0.25mmol advance preparation, is then added, is treated
Stir, be slowly dropped into heptamethyltrisiloxane HMTS 6g (mol ratio, the n of 5mL THF dilutionsAllyl alcohol：nHMTS=1.2), 4
~6s/d, after removing constant pressure funnel, 30 DEG C are heated to, is heated to reflux 4h.After question response terminates, revolving removes most of molten
Agent, surplus solution are separated with chromatographic column, and petroleum ether makees eluant, eluent, after collecting cut revolving removing solvent, obtain colorless oil
Hydroxypropyl heptamethyltrisiloxane (HPHMTS) product of shape, yield 72%.
(2) stannous octoate catalysis prepares HMTS-PCL
3.6g HPHMTS and 4.32g caprolactone are added in 50mL three-necked flask, is added under nitrogen protection
30mL toluene, 40mg octoate catalyst stannous is then added, is heated to 110 DEG C, 24 hours reaction time；After reaction terminates
Normal temperature is cooled to, adds a small amount of dichloromethane to dissolve product, is slowly dropped into the refrigerated methanol more than its 10 times of volumes (freezing first
Alcohol temperature is at 0~5 DEG C), white solid product is obtained, continues to be dissolved with a small amount of dichloromethane after filtering, precipitated in refrigerated methanol,
Repeatedly for three times, finally, product is placed in vacuum drying chamber and dried, obtain double block stabilizer HMTS-PCL white solids, production
Rate is 86%.
Embodiment 2
(1) Si―H addition reaction synthesis hydroxypropyl heptamethyltrisiloxane (HPHMTS)
1.9g allyl alcohol is added into three mouthfuls of reaction flasks under nitrogen protection and dries water removal 20mL tetrahydrochysene furan
Mutter, then add the Speier catalyst (0.5mol/L chloroplatinic acids/aqueous isopropanol) of 0.5mmol advance preparation, it is to be mixed
Uniformly, HMTS 6g (mol ratio, the n of 5mL THF dilutions are slowly dropped intoAllyl alcohol：nHMTS=1.2), 4~6s/d, constant pressure drop is removed
After liquid funnel, 20 DEG C are heated to, flow back 4h.After question response terminates, revolving removes most of solvent, and surplus solution is entered with chromatographic column
Row separation, petroleum ether make eluant, eluent, after collecting cut revolving removing solvent, obtain the silica of seven methyl of hydroxypropyl three of colorless oil
Alkane (HPHMTS) product, yield 68%.
(2) stannous octoate catalysis prepares HMTS-PCL
3.6g HPHMTS and 4.32g caprolactone are added in 50mL three-necked flask, is then added under nitrogen protection
Enter 30mL toluene.Then, 40mg octoate catalyst stannous is added, is heated to 120 DEG C, 48 hours reaction time.Reaction knot
Normal temperature is cooled to after beam, adds a small amount of dichloromethane lysate, (freezing is slowly added dropwise in the refrigerated methanol more than 10 times of volumes
Methanol temperature is at 0~5 DEG C), white solid product is obtained, continues to be dissolved with a small amount of dichloromethane after filtering, sunk in refrigerated methanol
Form sediment, repeatedly for three times, finally, product be placed in vacuum drying chamber and dried, obtain double block stabilizer HMTS-PCL white solids,
Yield is 72%.
Embodiment 3
(1) Si―H addition reaction synthesis hydroxypropyl heptamethyltrisiloxane (HPHMTS)
2.5g allyl alcohol is added into three mouthfuls of reaction flasks under nitrogen protection and dries water removal 20mL tetrahydrochysene furan
Mutter, then add the Speier catalyst (0.5mol/L chloroplatinic acids/aqueous isopropanol) of 0.2mmol advance preparation, it is to be mixed
Uniformly, HMTS 6g (mol ratio, the n of 5mL THF dilutions are slowly dropped intoAllyl alcohol：nHMTS=1.2), 5s/d, constant pressure addition leakage is removed
After bucket, 30 DEG C are heated to, is heated to reflux 4h.After question response terminates, revolving removes most of solvent, and surplus solution is entered with chromatographic column
Row separation, petroleum ether make eluant, eluent, after collecting cut revolving removing solvent, obtain the silica of seven methyl of hydroxypropyl three of colorless oil
Alkane (HPHMTS) product, yield 70%.
(2) stannous octoate catalysis prepares HMTS-PCL
3.6g HPHMTS and 5.4g caprolactone are added in 50mL three-necked flask, is then added under nitrogen protection
30mL toluene.Then, 40mg octoate catalyst stannous is added, is heated to 100 DEG C, 24 hours reaction time.Reaction terminates
After be cooled to normal temperature, add a small amount of dichloromethane lysate, be slowly added dropwise in the refrigerated methanol more than 10 times of volumes (freezing first
Alcohol temperature is at 0~5 DEG C), white solid product is obtained, continues to be dissolved with a small amount of dichloromethane after filtering, precipitated in refrigerated methanol,
Repeatedly for three times, finally, product is placed in vacuum drying chamber and dried, obtain double block stabilizer HMTS-PCL white solids, production
Rate is 80%.
Fig. 1 is the heptamethyltrisiloxane (HMTS) and hydroxypropyl heptamethyltrisiloxane obtained in embodiment 1
(HPHMTS) infrared spectrogram.Two spectrograms are in 793cm it can be seen from the infrared spectrum-1Stretched for Si-C keys in PDMS
Contracting vibration peak, 1058cm-1For the stretching vibration peak of Si-O keys in PDMS main chains, in 2958cm-1For methyl (CH3-) flexible shake
Dynamic peak.By contrast, the difference is that：HMTS spectrograms are in 2151cm-1There are the absworption peak of an obvious Si -- H bond, process and alkene
After propyl alcohol Si―H addition reaction, the absworption peak for obtaining Si -- H bond in target product HPHMTS infrared spectrum disappears, while in 3346cm-1
There is the absworption peak of hydroxyl, the product for showing synthesis is target product.Hence, it can be determined that the product of Si―H addition reaction is
3- hydroxypropyls heptamethyltrisiloxane (HPHMTS).
Fig. 2 is that the stannous octoate catalysis obtained in embodiment 1 prepares HMTS-PCL proton nmr spectra spectrogram.By Fig. 2
As can be seen that chemical shift is CDCl at 7.23ppm peak3Solvent peak；Belong at 4.01-4.04ppm peak on PCL segments
The methylene (- CH to connect with carboxylic epoxide2- O-C (O) -) on hydrogen (Ha+e) absworption peak, due to its connection electron-withdrawing group, make it
Chemical shift is located at low field；The peak of 2.25-2.29ppm positions is the absworption peak for the methylene hydrogen being connected on PCL segments with carboxyl
(-O-C(O)-CH 2-,Hd)；Most mid methylenes (- CH on PCL segments2-CH2-CH 2-CH2-CH2-) both ends are all electron-donating groups
Group, the chemical shift of its hydrogen absworption peak move apart from electron withdraw group farther out to High-Field, with reference to the spectrum analysis hydrogen (Hc) absorb
The chemical shift at peak is at 1.32-1.38ppm；The position of hydrogen absworption peak is among c and d at 1.60-1.63ppm, according to
HMTS-PCL molecular structures can determine that the position is f (- Si-CH2-CH 2-CH2- O-) and b (- CH2-CH 2-CH2-CH 2-CH2-)
Methylene hydrogen absworption peak, because it is nearer with respect to c apart from electron-withdrawing group, relative d and farther out；Because of the strong supplied for electronic effects of Si, make
The absworption peak of methylene hydrogen of being connected with silicon is located at low field 0.40-0.45ppm；The absworption peak of nigh hydrogen is methyl hydrogen on Si
Absworption peak.It is double block stabilizer HMTS-PCL by the provable product of spectrum analysis.
The active hydrogen of heptamethyltrisiloxane (HMTS) under Speier catalyst actions, carries out Si―H addition reaction with allyl alcohol
Reaction, generation hydroxypropyl heptamethyltrisiloxane (HPHMTS)；Under the catalysis of stannous octoate, drawn using the hydroxyl on HPHMTS
Caprolactone ring-opening polymerisation is sent out, synthesizes double block stabilizer HMTS-PCL.The preparation method is simple, and reaction condition is gentleer, instead
Short between seasonable, the product can be used for double block stabilizers that biological medicine material polymerize in supercritical fluid, available for overcritical
The dispersin polymerization of bio-medical material in fluid.
Claims (4)
1. a kind of double block stabilizer HMTS-PCL synthetic method, it is characterised in that utilize heptamethyltrisiloxane (HMTS)
Active hydrogen and allyl alcohol under Speier catalyst actions, carry out Si―H addition reaction, generate hydroxypropyl heptamethyltrisiloxane
(HPHMTS)；Under the catalysis of stannous octoate, trigger caprolactone (CL) ring-opening polymerisation using the hydroxyl on HPHMTS, synthesize seven first
Double block stabilizers of base trisiloxanes and polycaprolactone (HMTS-PCL)；Synthesis mechanism is as follows：
。
A kind of 2. double block stabilizer HMTS-PCL according to claim 1 synthetic method, it is characterised in that the side
Method comprises the following steps：
(1) add allyl alcohol into reaction flask under nitrogen protection and dry the tetrahydrofuran (THF) of water removal, then add
Speier catalyst, after stirring, 4~6s/d is slowly dropped into the heptamethyltrisiloxane diluted by tetrahydrofuran, at 20 DEG C
At~30 DEG C, reaction is stirred at reflux 3~5 hours；Wherein the mol ratio of allyl alcohol and heptamethyltrisiloxane is 1:1~2, seven first
The mass ratio of base trisiloxanes and Speier catalyst is 100~150:1；
(2) after the reaction of step (1) terminates, rotate, remaining solution is separated with chromatographic column after revolving, and petroleum ether elutes
Agent, after collecting cut revolving removing solvent, obtain hydroxypropyl heptamethyltrisiloxane colourless oil liquid；
(3) hydroxypropyl heptamethyltrisiloxane and caprolactone are added into flask, add toluene under nitrogen protection in flask,
Then stannous octoate catalyst is added, is heated to 100 DEG C~120 DEG C, 16~48 hours reaction time；The wherein methyl of hydroxypropyl seven
The mass ratio of trisiloxanes and caprolactone is 1:1~2, the mass ratio of hydroxypropyl heptamethyltrisiloxane and stannous octoate for 80~
100:1；
(4) after the reaction of step (3) terminates, be cooled to normal temperature, add methylene chloride make product dissolve after, be slowly dropped into more than its 10
In the refrigerated methanol (0~5 DEG C) of times volume, white solid product is obtained, continues to be dissolved with a small amount of dichloromethane after filtering, freezing
Precipitated in methanol, repeatedly for three times, finally, product is placed in vacuum drying chamber and dried, obtain double block stabilizer HMTS-PCL
White solid.
A kind of 3. double block stabilizer HMTS-PCL according to claim 1 synthetic method, it is characterised in that step
(1) mol ratio of allyl alcohol and heptamethyltrisiloxane is 1 in:1.2, the quality of heptamethyltrisiloxane and Speier catalyst
Than for 117:1,30 DEG C of reaction temperature, it is stirred at reflux the reaction time 4 hours.
A kind of 4. double block stabilizer HMTS-PCL according to claim 1 synthetic method, it is characterised in that its feature
It is, the mass ratio of hydroxypropyl heptamethyltrisiloxane and caprolactone is 1 in step (3):1.2, the silica of seven methyl of hydroxypropyl three
The mass ratio of alkane and stannous octoate is 90:1, heating-up temperature is 110 DEG C, and the reaction time is 24 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124563A (en) * | 2022-07-28 | 2022-09-30 | 广东微控生物科技有限公司 | Heptamethyl siloxane polyoxyethylene ether gallate and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316085A (en) * | 1996-05-23 | 1997-12-09 | Nippon Unicar Co Ltd | Reactive siloxane |
| CN103193963A (en) * | 2013-04-09 | 2013-07-10 | 大连大学 | Supercritical carbon dioxide dispersion polymerization stabilizer as well as preparation method and using method thereof |
-
2017
- 2017-08-23 CN CN201710729263.XA patent/CN107501531A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316085A (en) * | 1996-05-23 | 1997-12-09 | Nippon Unicar Co Ltd | Reactive siloxane |
| CN103193963A (en) * | 2013-04-09 | 2013-07-10 | 大连大学 | Supercritical carbon dioxide dispersion polymerization stabilizer as well as preparation method and using method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124563A (en) * | 2022-07-28 | 2022-09-30 | 广东微控生物科技有限公司 | Heptamethyl siloxane polyoxyethylene ether gallate and preparation method and application thereof |
| CN115124563B (en) * | 2022-07-28 | 2023-08-11 | 广东微控生物科技有限公司 | Seven-methyl siloxane polyoxyethylene ether gallate and preparation method and application thereof |
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Application publication date: 20171222 |
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| RJ01 | Rejection of invention patent application after publication |