CN105131268B - Application of iron powder/halide in catalysis of epsilon-caprolactone ring-opening polymerization reaction - Google Patents
Application of iron powder/halide in catalysis of epsilon-caprolactone ring-opening polymerization reaction Download PDFInfo
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- CN105131268B CN105131268B CN201510488607.3A CN201510488607A CN105131268B CN 105131268 B CN105131268 B CN 105131268B CN 201510488607 A CN201510488607 A CN 201510488607A CN 105131268 B CN105131268 B CN 105131268B
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- caprolactone
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Abstract
The invention discloses application of iron powder/halide in catalysis of epsilon-caprolactone ring-opening polymerization reaction. Specifically, the process includes: under the protection of inert gas, according to a mole ratio of 50-250:1:0.5-3 between epsilon-caprolactone, iron powder and halide, adding iron powder, halide, epsilon-caprolactone and a solvent into a reaction container in order, conducting sealing, then carrying out reaction at 90-120DEG C for 12-48h; at the end of the reaction, cooling the reaction system to room temperature, adding tetrahydrofuran to conduct dilution, also using a mixed solution of anhydrous methanol and dilute hydrochloric acid to conduct sedimentation, and performing filtering and drying to obtain polycaprolactone. The iron powder/halide catalyst provided by the invention has very high catalytic activity in epsilon-caprolactone ring-opening polymerization reaction, so that the epsilon-caprolactone ring-opening polymerization reaction has very high yield, and the obtained polymer has narrow molecular weight distribution.
Description
Technical field
The invention belongs to chemical field, it is related to iron powder/halides in catalysisεIn-caprolactone ring-opening polymerization
Application.
Background technology
In recent years, due to degradability aliphatic polyester have in bio-medical material, pharmacy and agriculture field wide
Application prospect, it causes the great interest of researcher.Wherein, polycaprolactone has good water-disintegrable, mechanicalness
Can and biocompatibility, be widely used in operation suture thread, manufacture hone lamella, tissue renovation material, drug carrier material and
Other biological medical material.
Polycaprolactone typically byε- caprolactone metal complex (as stannum, aluminum, rare earth metal, alkaline-earth metal and some
The coordination compounds such as transition metal) catalyst exist under conditions of by ring-opening polymerization be obtained.However, these catalyst great majority
Relatively costly, preparation process is loaded down with trivial details, be difficult preservation；In addition, metal used also has certain toxicity, in the purification mistake of polymer
It is very difficult in journey, except clean, so that prepared macromolecular material product has potentially danger, limit it in biological doctor
Application in the fields such as medicine.
Exploration has biocompatibility, the catalyst nontoxic to human body has become as the study hotspot of people.Wherein, ferrum unit
Element is trace element needed by human, is also one of metal distributed more widely on the earth, and therefore iron catalyst is a kind of great
The catalyst of exhibition potentiality.At present, a lot of seminars be devoted to synthesize various iron catalysts (referring to gowda r. r.,
chakraborty d.,j. mol. catal. a-chem.,2009, 301:84-92；mcguinness d. s.,
marshall e. l.,et. al., j. polym. sci. pol. chem.,2003, 41:3798-3803；
kricheldorf h. r., serra a.,polym. bull.,1985, 14:497-502；kricheldorf h. r.,
boettcher c.,makromol. chem.,1993, 194:463-473；kricheldorf h. r., damrau d.
o.,macromol. chem. phys.,1997, 198:1767-1774；stolt m., södergård a.,macromolecules,1999, 32:6412-6417；hege c. s., schiller s. m.,green chem.,
2014, 16:1410-1416；chen m.-z., sun h.-m.,et. al., j. organomet. chem.,2006,
691:2489-2494.), but these iron catalysts all have the shortcomings that building-up process is complicated, unstable, are difficult to preserve.Cause
This, explore active height, avirulence, prepare convenient, low cost and be easy to the iron catalyst preserving, and use it for polycaprolactone
Preparation, tool is of great significance.
Content of the invention
For above-mentioned situation, the invention discloses iron powder/halides are in catalysisεAnswering in-caprolactone ring-opening polymerization
With.In the present invention, the iron powder/halides as catalyst can efficiently be catalyzedεIt is anti-that-caprolactone monomer carries out ring-opening polymerisation
Should, and then obtain molecular weight height, the polycaprolactone of narrow molecular weight distribution.
Specifically, the invention provides a kind of be catalyzed using iron powder/halidesε- caprolactone ring-opening polymerization is making
The method of standby polycaprolactone, the method comprises the following steps:
Under inert gas shielding, according toε- caprolactone: iron powder: the mol ratio of halides=50 ~ 250:1:0.5 ~ 3, to
Sequentially add in reaction vessel iron powder, halides,ε- caprolactone and solvent, sealing is reacted 12 ~ 48 hours after 90 ~ 120 DEG C；
After reaction terminates, reaction system is cooled to room temperature, adds oxolane dilution, and the mixing with absolute methanol and dilute hydrochloric acid is molten
Liquid precipitate, filters, and is dried, obtains polycaprolactone.
Preferably, in the above-mentioned methods, any one in nitrogen, helium, neon, argon of described noble gases,
Preferably nitrogen.
Preferably, in the above-mentioned methods, described reaction vessel is any vessel being suitable for carrying out anhydrous and oxygen-free reaction, excellent
Select Xi Laike (schlenk) bottle.
Preferably, in the above-mentioned methods, described solvent is toluene.
Preferably, in the above-mentioned methods, describedεMol ratio between-caprolactone, iron powder, halides is 100:1:1.
Preferably, in the above-mentioned methods, described iron powder is the ferrous metal simple substance existing in powder form, purity be 98% with
On.
Preferably, in the above-mentioned methods, described halides are selected from 2- bromo acid glycol ester (2-hydroxyethyl
2-bromoisobutyrate, hebib), 2- isobutyl ethyl bromide (ethyl 2-bromoisobutyrate, ebib), bromine
For tertiary butane (2-bromo-2-methylpropane, bmp), cylite (benzyl bromide, bnbr), chloroform
(trichloromethane, chcl3) in any one (structure is as follows):
.
As exception, in the above-mentioned methods, when described halides are chloroform, it uses simultaneously as solvent, no
Other solvents need to be added.
Preferably, in the above-mentioned methods, the temperature of described reaction is 110 DEG C.
Preferably, in the above-mentioned methods, the time of described reaction is 24 hours.
Preferably, in the above-mentioned methods, after adding described iron powder and halides and described addingε- own interior
Before ester, according to polyhydroxyl initiator: the mol ratio of iron powder=1:1, add polyhydroxyl initiator, wherein institute in described reaction vessel
State polyhydroxyl initiator and be selected from benzyl alcohol, isopropanol, any one in water, preferably benzyl alcohol.
As exception, in the above-mentioned methods, when described halides are that 2- bromo acid glycol ester is (a kind of as implied above
While there is the difunctional type compound of bromine atoms and hydroxyl) when, it uses simultaneously as polyhydroxyl initiator, need not add again
Enter other polyhydroxyl initiator.
Due to the utilization of technique scheme, the present invention compared with prior art has the advantage that
(1) the invention discloses the iron powder/halides as catalyst are being catalyzedεIn-caprolactone ring-opening polymerization
Application, is that the synthesis of polycaprolactone provides new selection；
(2) iron powder used by the present invention is ferrous metal simple substance, and it is trace element needed by human, and human body is produced
Toxicity is relatively low, and safety is higher, is one of metal distributed more widely on the earth again, and low price is it is easy to preserve；
(3) halides used by the present invention are industrially readily available, and cost is relatively low；
(4) catalyst used by the present invention is applied toε- caprolactone ring-opening polymerization, can play higher catalysis and live
Property, and obtaining higher yield, prepared polycaprolactone also has narrower molecular weight distribution.
Brief description
Fig. 1 is iron powder in the present invention/halides catalysisε(roh draws the schematic diagram of-caprolactone ring-opening polymerization for hydroxyl
Send out agent, fe is iron powder, r ' x is halides).
Fig. 2 is iron powder in embodiment 1/2- bromo acid glycol ester catalysisεThe kinetics of-caprolactone ring-opening polymerisation
Curve.
Fig. 3 is iron powder in embodiment 1/2- bromo acid glycol ester catalysisεThe yield of-caprolactone ring-opening polymerisation with
The molecular weight of resulting polymers and the graph of a relation of molecular weight distributing index.
Fig. 4 is iron powder in embodiment 1/2- bromo acid glycol ester catalysisεObtained by the ring-opening polymerisation of-caprolactone
Polymer1H-nmr spectrogram.
Fig. 5 is embodiment 2 to iron powder in embodiment 5/halides catalysisεPolymer obtained by the ring-opening polymerisation of-caprolactone
's1H-nmr spectrogram (to add as a example the polymer of the benzyl alcohol gained of polyhydroxyl initiator, belongs to each absworption peak institute right
The hydrogen atom answered).
Specific embodiment
With reference to specific embodiment, the present invention is made and further describing.
Embodiment 1: iron powder/2- bromo acid glycol ester is in catalysisεApplication in the ring-opening polymerisation of-caprolactone.
Under nitrogen protection, iron powder (5.6 ~ 11.2 mg, 0.1 ~ 0.2 mmol), 2- bromine are sequentially added in schlenk bottle
For isopropylformic acid. glycol ester (14.18 ~ 28.36 μ l, 0.1 ~ 0.2 mmol),ε- caprolactone (1.11 ~ 2.77 ml, 10 ~ 25
Mmol) and toluene (1 ml), it is then placed in being reacted (24 ~ 28 h) in 110 DEG C of oil baths.After reaction terminates, reactant liquor is cold
But to room temperature, add oxolane dilution, and the mixed solution precipitation with absolute methanol and dilute hydrochloric acid, filter, be dried, gathered
Caprolactone.
Parallel under different reaction conditions prepare polycaprolactone, the data obtaining is as follows:
As can be seen from the above table, the catalyst in embodiment 1 (iron powder/2- bromo acid glycol ester) have very high
Catalysis activity, makesε- caprolactone ring-opening polymerization has very high yield, and resulting polymers have narrower molecular weight and divide
Cloth.As shown in Figures 2 and 3, existεWhen-caprolactone, iron powder, the mol ratio of 2- bromo acid glycol ester are 100:1:1, should
(no chain termination, no chain tra nsfer, the time ratio that concentration of active center keeps constant completes the feature of the active polymerization of polyreaction
The required time long several times of reaction).
Embodiment 2: iron powder/2- isobutyl ethyl bromide is in catalysisεApplication in the ring-opening polymerisation of-caprolactone.
Under nitrogen protection, iron powder (5.6 mg, 0.1 mmol), 2- bromo acid are sequentially added in schlenk bottle
Ethyl ester (14.44 μ l, 0.1 mmol), the benzyl alcohol (10.40 μ l, 0.1 mmol) as polyhydroxyl initiator or isopropanol
(7.65 μ l, 0.1 mmol) or water (1.80 μ l, 0.1 mmol),ε- caprolactone (1.11 ml, 10 mmol), toluene (1
Ml), it is then placed in being reacted (24 h) in 110 DEG C of oil baths.After reaction terminates, reactant liquor is cooled to room temperature, adds tetrahydrochysene
Furan dilutes, and the mixed solution precipitation with absolute methanol and dilute hydrochloric acid, filters, is dried, obtains polycaprolactone.
Do not use or use parallel under conditions of different polyhydroxyl initiator prepare polycaprolactone, the data obtaining is as follows
Shown:
As can be seen from the above table, the catalyst in embodiment 2 (iron powder/2- isobutyl ethyl bromide) is in catalysisε- own interior
There is in ester ring-opening polymerization very high catalysis activity, the molecular weight of resulting polymers and theoretical molecular are more or less the same, and
And there is narrower molecular weight distribution, and during with benzyl alcohol for initiator, yield highest.
Embodiment 3: iron powder/tert-bromo butane is in catalysisεApplication in the ring-opening polymerisation of-caprolactone.
Under nitrogen protection, iron powder (5.6 mg, 0.1 mmol), tert-bromo butane are sequentially added in schlenk bottle
(11.23 μ l, 0.1 mmol), benzyl alcohol (10.40 μ l, 0.1 mmol, or without),ε- caprolactone (1.11 ml, 10
Mmol), toluene (1 ml), is then placed in being reacted (24 h) in 110 DEG C of oil baths.After reaction terminates, reactant liquor is cooled to
Room temperature, adds oxolane to dilute, and is precipitated with the mixed solution of absolute methanol and dilute hydrochloric acid, filters, is dried, and obtains poly- own interior
Ester.
When being not added with polyhydroxyl initiator, the molecular weight of resulting polymers is 15250 g/mol, and molecular weight distributing index is
1.06(is narrower), yield is 60.0%；When adding polyhydroxyl initiator, the molecular weight of resulting polymers is 13070 g/mol, point
Son amount profile exponent is that 1.13(is narrower), yield is 92.0% hence it is evident that higher than the yield that is not added with during polyhydroxyl initiator, illustrates now
Catalyst (iron powder/tert-bromo butane) catalysisεThere is in-caprolactone ring-opening polymerization higher catalysis activity.
Embodiment 4: iron powder/cylite is in catalysisεApplication in the ring-opening polymerisation of-caprolactone.
Under nitrogen protection, iron powder (5.6 mg, 0.1 mmol), cylite (11.88 are sequentially added in schlenk bottle
μ l, 0.1 mmol), benzyl alcohol (10.40 μ l, 0.1 mmol, or without),ε- caprolactone (1.11 ml, 10 mmol),
Toluene (1 ml), is then placed in being reacted (24 h) in 110 DEG C of oil baths.After reaction terminates, reactant liquor is cooled to room temperature, plus
Enter oxolane dilution, and the mixed solution precipitation with absolute methanol and dilute hydrochloric acid, filter, be dried, obtain polycaprolactone.
When being not added with polyhydroxyl initiator, the molecular weight of resulting polymers is 4410 g/mol, and molecular weight distributing index is
1.04(is very narrow), yield is that 24.1%(is relatively low)；When adding polyhydroxyl initiator, the molecular weight of resulting polymers is 9460 g/
Mol, molecular weight distributing index is that 1.14(is narrower), yield is 87.8% hence it is evident that higher than the yield that is not added with during polyhydroxyl initiator, says
Bright catalyst (iron powder/cylite) now is in catalysisεThere is in-caprolactone ring-opening polymerization higher catalysis activity.
Embodiment 5: iron powder/chloroform is in catalysisεApplication in the ring-opening polymerisation of-caprolactone.
Under nitrogen protection, iron powder (5.6 mg, 0.1 mmol), chloroform (1 are sequentially added in schlenk bottle
Ml), benzyl alcohol (10.40 μ l, 0.1 mmol, or without),ε- caprolactone (1.11 ml, 10 mmol), toluene (1
Ml), it is then placed in being reacted in 110 DEG C of oil baths.After reaction terminates, reactant liquor is cooled to room temperature, adds oxolane dilute
Release, and the mixed solution precipitation with absolute methanol and dilute hydrochloric acid, filter, be dried, obtain polycaprolactone.
When being not added with polyhydroxyl initiator, the molecular weight of resulting polymers is 20180 g/mol, and molecular weight distributing index is
1.28(is narrower), yield is 89.0%；When adding polyhydroxyl initiator, the molecular weight of resulting polymers is 14410 g/mol, point
Son amount profile exponent is that 1.21(is narrower), yield is 100% hence it is evident that higher than the yield that is not added with during polyhydroxyl initiator, illustrates now
Catalyst (iron powder/chloroform) is in catalysisεThere is in-caprolactone ring-opening polymerization higher catalysis activity.
Pass through1H-nmr characterizes, the difunctional hydroxyl bromide 2- bromo acid glycol ester in embodiment 1
Really serve the initiation (referring to Fig. 4) of polyhydroxyl initiator, in the nuclear magnetic spectrogram of resulting polymers, occur in that 2- bromo is different
Proton characteristic peak in butanoic acid glycol ester；Equally, embodiment 2 also plays to polyhydroxyl initiator used in embodiment 5 and draws
(referring to Fig. 5) is used in outbreak, occurs in that the proton characteristic peak in benzyl in the nuclear magnetic spectrogram of resulting polymers.
In sum, iron powder/halides are in catalysisεThere is in the application of-caprolactone ring-opening polymerization higher catalysis
Activity, the molecular weight of resulting polymers and theoretical molecular are more or less the same, and molecular weight distribution is narrower, and polyhydroxyl initiator exists
When reaction yield higher than there is no the yield in the presence of polyhydroxyl initiator.
Claims (9)
1. a kind of method preparing polycaprolactone using iron powder/halides catalysis 6-caprolactone ring-opening polymerization, it includes
The following step:
Under inert gas shielding, according to 6-caprolactone: iron powder: the mol ratio of halides=50～250:1:0.5～3, to anti-
Answer and in container, sequentially add iron powder, halides, 6-caprolactone and solvent, sealing is reacted 12～48 hours after 90～120 DEG C；Instead
After should terminating, reaction system is cooled to room temperature, adds oxolane dilution, and the mixed solution with absolute methanol and dilute hydrochloric acid
Precipitation, filters, and is dried, obtains polycaprolactone；
Wherein: described halides are selected from 2- bromo acid glycol ester, 2- isobutyl ethyl bromide, tert-bromo butane, bromination
Any one in benzyl, chloroform.
2. method according to claim 1 is it is characterised in that mol ratio between described 6-caprolactone, iron powder, halides
For 100:1:1.
3. method according to claim 1 is it is characterised in that described noble gases are selected from nitrogen, helium, neon, argon
In any one.
4. method according to claim 1 is it is characterised in that described solvent is toluene.
5. method according to claim 1 is it is characterised in that described iron powder is the ferrous metal list existing in powder form
Matter, purity is more than 98%.
6. method according to claim 1 it is characterised in that when described halides be chloroform when, its simultaneously as
Solvent uses, and need not add other solvents.
7. it is characterised in that the temperature of described reaction is 110 DEG C, the time is 24 hours to method according to claim 1.
8. method according to claim 1 is it is characterised in that after adding described iron powder and halides, and plus
Before entering described 6-caprolactone, according to polyhydroxyl initiator: the mol ratio of iron powder=1:1, add hydroxyl in described reaction vessel
Initiator, any one in benzyl alcohol, isopropanol, water of wherein said polyhydroxyl initiator.
9. method according to claim 8 is it is characterised in that working as described halides is 2- bromo acid glycol ester
When, it uses simultaneously as polyhydroxyl initiator, need not add other polyhydroxyl initiator.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250325A (en) * | 2010-05-19 | 2011-11-23 | 中国石油化工集团公司 | Method for preparing poly (epsilon-caprolactone) |
| CN103910763A (en) * | 2014-01-06 | 2014-07-09 | 苏州大学 | Water-soluble iron complex and its preparation method and use |
| CN104557847A (en) * | 2015-01-09 | 2015-04-29 | 武汉理工大学 | Production method for depolymerising polycaprolactone by using cationic catalyzing method |
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| FI103581B1 (en) * | 1996-11-11 | 1999-07-30 | Neste Oy | A process for preparing polyhydroxy acids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250325A (en) * | 2010-05-19 | 2011-11-23 | 中国石油化工集团公司 | Method for preparing poly (epsilon-caprolactone) |
| CN103910763A (en) * | 2014-01-06 | 2014-07-09 | 苏州大学 | Water-soluble iron complex and its preparation method and use |
| CN104557847A (en) * | 2015-01-09 | 2015-04-29 | 武汉理工大学 | Production method for depolymerising polycaprolactone by using cationic catalyzing method |
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