CN105367760B - A kind of method for preparing poly epsilon caprolactone lactone - Google Patents
A kind of method for preparing poly epsilon caprolactone lactone Download PDFInfo
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- CN105367760B CN105367760B CN201510807235.6A CN201510807235A CN105367760B CN 105367760 B CN105367760 B CN 105367760B CN 201510807235 A CN201510807235 A CN 201510807235A CN 105367760 B CN105367760 B CN 105367760B
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Abstract
The present invention discloses a kind of preparation method of poly epsilon caprolactone lactone, is by the way that ε caprolactones are mixed in proportion with alkanol molecule amount conditioning agent, 1 is added（4 sulfonic groups）The methylpyrazine tetrafluoroborate of butyl 3 or 1（4 sulfonic groups）One kind in the methyl imidazolium tetrafluoroborate of butyl 3 makees catalyst, under 60 180 degrees, and ring-opening polymerisation is carried out under the conditions of anhydrous and oxygen-free and obtains poly epsilon caprolactone lactone.
Description
Technical field
The invention belongs to polymeric material field, and in particular to the method for preparing poly-epsilon-caprolactone.
Background technology
Poly-epsilon-caprolactone has good pliability, processability and biodegradable, particularly with shape memory,
There is preferable application prospect in fields such as the positioning board for radiotherapy of biomedical sector, adhesive tape, bandage, rectifiers, also used extensively
Carry out modified toughened other high polymer materials such as PLA etc..The low molecule amount polycaprolactone of terminal hydroxy group is used as new and high-grade poly- ammonia
Ester material has good elasticity, substitutes polyethers in fields such as high-end adhesive, polyurethane foam, sponge and polyurethane paints
Polyalcohol.
The preparation method of poly-epsilon-caprolactone existing substantial amounts of research at present, wherein main method is being urged with 6-caprolactone
Agent effect is lower to carry out ring-opening polymerisation preparation, and various catalyst turn into the focus of research.Such as CN1814644,
US5235031, US5357034, US4057537 etc., which are reported, carries out catalysis 6-caprolactone and the third friendship with metallic catalysts such as pink salts
Ester carries out ring-opening polymerisation and prepares poly-epsilon-caprolactone and PLA the polymeric material that still prepared by this kind of method due to extremely difficult removing
Metal residue, thus some specific fields such as biomedical and microelectronics field can not be applied to.Connor etc.
（Angewandte Chemie International Edition, 2001,40,2712-2715) propose only to use organic catalyst
To carry out ring-opening polymerisation, and attempt with DMAP as catalyst.Then occur in that organic phosphine, difunctional sulphur again
Urea amine, guanidine, amidine class and N- heterocycle carbine class catalyst preparations obtain metal-free poly-epsilon-caprolactone.CN104530393
Also report prepared with nonmetallic organic catalyst ring-opening polymerization of lactone by catalysis metal-free PLA and poly- ε-oneself
Lactone etc..
The content of the invention
In order to meet requirement of the fields such as biomedical sector to material and it is simple, gentle, efficiently synthesize poly-epsilon-caprolactone
Requirement, it is an object of the invention to provide a kind of new catalyst without heavy metal, be catalyzed the ring-opening polymerisation of 6-caprolactone, system
It is standby to obtain the poly-epsilon-caprolactone without heavy metal.
The object of the present invention is achieved like this：
The preparation method of this poly-epsilon-caprolactone, is that 6-caprolactone is mixed in proportion with alkanol molecule amount conditioning agent, plus
Enter catalyst, under 60-180 degree, under the conditions of anhydrous and oxygen-free（Under inert gas shielding or vacuum）Ring-opening polymerisation is carried out, during polymerization
Between be 1-24 hour, polymerization unit be high molecular polymerization common equipment, can be interval can also be continuous device, reach need
Purified after the degree of polymerization requirement wanted with conventional method and remove unreacted monomer and impurity, obtain poly-epsilon-caprolactone.
The preparation method of this poly-epsilon-caprolactone, used catalyst is the ion liquid compound of bifunctional group, specifically
It is 1-（4- sulfonic groups）Butyl -3- methylpyrazines tetrafluoroborate or 1-（4- sulfonic groups）Butyl -3- methylimidazole tetrafluoro boric acids
One kind in salt, consumption is 0.01-10%.
The structure of catalyst is as follows：
1-（4- sulfonic groups）Butyl -3- methylpyrazine tetrafluoroborates
1-（4- sulfonic groups）Butyl -3- methyl imidazolium tetrafluoroborates
The preparation method of this poly-epsilon-caprolactone, molecular weight regulator is multicomponent alcoholics compound, such as ethylene glycol, the third two
One kind in alcohol, glycerine, butanediol and 1,2-PD, its consumption is 0.01-10%, with specific reference to required polycaprolactone
Molecular size range is determined.
Outer unless otherwise indicated, involved molecular weight is represented with weight average molecular weight in the present invention, and its value is using solidifying
Glue penetration chromatogram（GPC）Determine.
Embodiments of the invention are given below, the present invention is specifically described by embodiment.Be necessary it is pointed out here that
, embodiment is served only for that the present invention is further detailed, it is impossible to be interpreted as limiting the scope of the invention, should
The person skilled in the art in field can make some nonessential modifications and adaptations according to the content of the invention described above.
Embodiment
Embodiment 1
In 1 liter of vial, 300 grams of 6-caprolactones of addition, 2 grams of ethylene glycol, after being replaced three times with high pure nitrogen, nitrogen is protected
Shield is lower to add 0.05 gram of 1-（4- sulfonic groups）Butyl -3- methyl imidazolium tetrafluoroborates, are heated to 120-140 degree and react 12 hours
After be cooled to room temperature, with 2000 milliliters of chloroform dissolved products, 280 grams of poly-epsilon-caprolactone is obtained with 5000 milliliters of ethanol precipitations, pass through
GPC determines weight average molecular weight 30,000, molecular weight distribution 1.3.
Embodiment 2
15 kilograms of 6-caprolactone is added in the reactor of 20 liters of stainless steel band stirrings, 0.15 kilogram of butanediol is added, fills
Nitrogen simultaneously displaced air three times, nitrogen protection is lower to add 1-（4- sulfonic groups）75 grams of butyl -3- methylpyrazines tetrafluoroborate, in
130-150 degree polymerisation 12 hours, then vacuum at such a temperature（Vacuum 1-10mmHg）Unreacted monomer is removed, is obtained
To 14.5 kilograms of poly-epsilon-caprolactones, weight average molecular weight 10,000, molecular weight distribution 1.2 are determined through GPC.
Embodiment 3
15 kilograms of 6-caprolactone is added in the reactor of 20 liters of stainless steel band stirrings, 0.75 kilogram of 1,2-PD fills
Nitrogen simultaneously displaced air three times, nitrogen protection is lower to add 1-（4- sulfonic groups）15 grams of butyl -3- methylpyrazines tetrafluoroborate,
90-120 degree polymerize 12 hours, then vacuum at such a temperature（Vacuum 1-10mmHg）Unreacted monomer and impurity are removed,
14.8 kilograms of poly-epsilon-caprolactones are obtained, weight average molecular weight 2500, molecular weight distribution 1.24 are determined through GPC.
Embodiment 4
15 kilograms of 6-caprolactone, 0.3 kilogram of glycerine, inflated with nitrogen are added in the reactor of 20 liters of stainless steel band stirrings
And displaced air three times, nitrogen protection is lower to add 1-（4- sulfonic groups）0.15 kilogram of butyl -3- methyl imidazolium tetrafluoroborates, in
150-170 degree polymerisation 8 hours, then vacuum at such a temperature（Vacuum 1-10mmHg）Remove unreacted monomer and miscellaneous
Matter, obtains 14 kilograms of poly-epsilon-caprolactones, and weight average molecular weight 5000, molecular weight distribution 1.3 are determined through GPC.
Embodiment 5
15 kilograms of 6-caprolactone is added in the reactor of 20 liters of stainless steel band stirrings, 20 grams of propane diols, inflated with nitrogen is added
And displaced air three times, then add 1-（4- sulfonic groups）20 grams of butyl -3- methylpyrazines tetrafluoroborate, in 140-150 degree
Polymerisation 12 hours, then vacuum at such a temperature（Vacuum 1-10mmHg）Unreacted monomer is removed, 14.5 are obtained public
Jin poly-epsilon-caprolactone, weight average molecular weight 100,000, molecular weight distribution 2.3 are determined through GPC.
Claims (1)
1. a kind of preparation method of poly-epsilon-caprolactone, it is characterized in that by 6-caprolactone and alkanol molecule amount conditioning agent in proportion
Mixing, adds bifunctional group ionic-liquid catalyst, under 60-180 degree, ring-opening polymerisation is carried out under the conditions of anhydrous and oxygen-free, gathers
The conjunction time is 1-24 hours, obtains poly-epsilon-caprolactone；
The bifunctional group ionic-liquid catalyst is specifically 1-（4- sulfonic groups）Butyl -3- methylpyrazines tetrafluoroborate or
1-（4- sulfonic groups）Butyl -3- methyl imidazolium tetrafluoroborates, consumption is 0.01-10%, and the structure of catalyst is as follows：
1-（4- sulfonic groups）Butyl -3- methylpyrazine tetrafluoroborates
1-（4- sulfonic groups）Butyl -3- methyl imidazolium tetrafluoroborates；
The alkanol molecule amount conditioning agent is ethylene glycol, propane diols, glycerine, butanediol or 1,2-PD, and its consumption is
0.01-10%。
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| CN107141457B (en) | 2017-05-19 | 2019-12-20 | 南京工业大学 | Method for preparing polylactone by ring opening |
| CN109851764B (en) * | 2019-01-30 | 2021-07-23 | 南京工业大学 | Preparation method of polylactone |
| CN111621128A (en) * | 2020-06-22 | 2020-09-04 | 广安长明高端产业技术研究院 | Preparation method of graphene oxide grafted polycaprolactone, toughening agent and 3D printing consumable |
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| CN1168756C (en) * | 2002-02-10 | 2004-09-29 | 复旦大学 | Method for preparing macromolecular weight branched polycaprolactone |
| CN102250325A (en) * | 2010-05-19 | 2011-11-23 | 中国石油化工集团公司 | Method for preparing poly (epsilon-caprolactone) |
| CN104530393B (en) * | 2015-01-12 | 2016-06-08 | 南京工业大学 | A kind of method preparing polylactone |
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