CN109810246A - A kind of low temperature polycaprolactone preparation method that fusing point is controllable - Google Patents
A kind of low temperature polycaprolactone preparation method that fusing point is controllable Download PDFInfo
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- CN109810246A CN109810246A CN201811602996.8A CN201811602996A CN109810246A CN 109810246 A CN109810246 A CN 109810246A CN 201811602996 A CN201811602996 A CN 201811602996A CN 109810246 A CN109810246 A CN 109810246A
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Abstract
The present invention relates to the methods of polycaprolactone, and in particular to a kind of low temperature polycaprolactone preparation method that fusing point is controllable.The following steps are included: caprolactone, initiator and modified monomer are mixed, are dehydrated, catalyst is added afterwards, carries out bulk polymerization under inert gas protection, and slough low molecule through high vacuum in molten state, obtains white solid state polycaprolactone after cooling.Present invention process is simple, is designed by formula, and the fusing point of polymer can be controlled in 40-55 DEG C, and narrow molecular weight distribution, and mechanical performance is excellent, has good processing performance.
Description
Technical field
The present invention relates to the methods of polycaprolactone, and in particular to a kind of low temperature polycaprolactone preparation method that fusing point is controllable.
Background technique
Polycaprolactone (PCL) has good biological degradability, biocompatibility and nontoxicity, and is widely used as medical
Biodegradation material and controlled drug delivery system can be compatible with a variety of common plastics, 6-12 months under natural environment
It is degradable.In addition, PCL also has good shape memory temperature control property, be widely used in pharmaceutical carrier, plasticizer, can
Degradative plastics, nanofiber spinning, the production of moulding material and manufacture field.
PCL is a kind of high polymer of half crystal form, and crystallinity is 45% or so, and external appearance characteristic is like medium density polyethylene, cream
White has wax sense.Fusing point is at 60 DEG C or so, and glass transition temperature is about -60 DEG C, and mechanical property and polyolefins are seemingly.
PCL be as 6-caprolactone monomer existing for the initiator under the conditions of ring-opening polymerisation obtained by, have 5 nonpolar one CH2 of methylene
One and 1 polar one COO mono- of ester bond constitutes its duplicate structural unit, and the C-C key and C-O bond energy in strand are enough freely
Rotation, such structure make PCL have good flexibility, can be copolymerized and be blended with many polymer.While it
With good thermal stability, decomposition temperature is 350 DEG C, other polyester are generally 250 DEG C.
In the production and processing of polycaprolactone (PCL) product, sometimes require the fusing point of polymer relatively low, so just
In production and processing, to reduce processing cost or reach the mechanical performance of different requirements.To meet above-mentioned requirements, in the prior art
Generally using the method for different polycaprolactones mixing.
In recent years the report in relation to caprolactone polymerization oneself have much, usually cause caprolactone ring-opening polymerisation system include:
(a) active hydrogen causes system (b) cationic catalyst (c) anionic catalyst d () polycomplexation mould assembly catalyst (e) light
Activated catalyst: i.e. catalyst just has certain activity, such as Ph4P, FeCl4 etc. after photoactivation.Furthermore caprolactone can be with
Light initiation polymerization, gamma Rays polymerization and microwave radiation polymerization etc..
Patent CN104592501A discloses a kind of preparation method of polycaprolactone, is to urge with amido anilino- lithium compound
Agent obtains the polymer of narrow molecular weight distribution using polymerisation in solution.Patent CN106496538A discloses a kind of high molecular weight
The synthetic method of polycaprolactone mixes lewis acid and initiator hydroxyl alcohol, shape in a solvent using lewis acid as catalyst
Caprolactone monomer ring-opening polymerisation is attacked at negative oxygen ion, which can carry out that heavy polymer is made at room temperature.More than
The method that two patents are all made of polymerisation in solution requires to carry out processing extraction polymer after reaction, and solvent retains can be to polymerization
Purity generates adverse effect.
Summary of the invention
The present invention provides a kind of preparation methods of the controllable polycaprolactone of fusing point, and this method is easy to operate, are set by formula
Meter, the fusing point of polymer can be controlled in 40-55 DEG C, and narrow molecular weight distribution, and mechanical performance is excellent, have good processability
Energy.
The present invention adopts the following technical scheme that realization:
1000 parts of caprolactone, 0.2-200 parts of modified monomer, initiator, 50-400 parts, 0.2-1.5 parts of catalyst, it is described to change
Property monomer includes at least one of glycolide, lactide, carbonic ester；The initiator includes polyethylene glycol, polypropylene glycol, gathers
At least one of tetrahydrofuran；The catalyst be dibutyl tin dilaurate, stannous octoate, dilaurate dioctyl tin,
One of tributylphosphine, dimethylphenylphosphine, N- heterocycle carbine compound.
In above-mentioned preparation method, the modified monomer is cyclic ester monomer, including one in glycolide, lactide, carbonic ester
Kind or two kinds.
In above-mentioned preparation method, the initiator is polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran
At least one of (PTMG), preferred molecular weight is the initiator of 2000-8000g/mol.
In above-mentioned preparation method, the catalyst is dibutyl tin dilaurate, stannous octoate, dilaurate dioctyl
One of tin, tributylphosphine, dimethylphenylphosphine, heterocyclic nitrogen compound, preferably octanoic acid stannous or N- heterocycle carbine.
The preparation method of polycaprolactone, comprising the following steps: the preceding place of raw material caprolactone, initiator and modified monomer
Reason；Catalyst, temperature-programmed reaction are added into system；Reactant post-processes after reaction.
In above-mentioned reaction, pre-treatment, which refers to, is dehydrated raw material at 80-100 DEG C, pressure 10-50Pa, and mixes
Uniformly mixing.
In above-mentioned reaction, Temperature Programmed Processes are: 120 DEG C of reactions 1h, 140 DEG C of reactions 1h, 160 DEG C of reaction 2-4h, reaction
It carries out under inert gas protection.
In above-mentioned reaction, reactant post-processing approach is in vacuum degree lower than 20Pa devolatilization 1h.
Present invention is characterized in that providing a kind of PCL synthetic method, reaction process is solvent-free, can prepare high molecular weight
Polymer, this method simple process can prepare the product of different melting points, and the more conventional PCL of product fusing point is low.
Specific embodiment
It will carry out the specific description present invention using embodiment below, but the present invention is not limited by following embodiment.
Embodiment 1
1000g caprolactone, 30g glycolide and 205gPEG (PEG molecular weight is 8000g/mol) are put into reactor,
80 DEG C, dehydration mixing 1h under 50Pa pressure, after octoate catalyst stannous 0.6g is added under inert gas protection, system starts to rise
Temperature is warming up to 120 DEG C of reaction 1h, then is warming up to 140 DEG C of reaction 1h, finally in 160 DEG C of reaction 4h, then in the case where pressure is 10Pa
Devolatilization 1h obtains white solid after discharging is cooling.55.2 DEG C of fusing point.
Embodiment 2
1000g caprolactone, 300g glycolide and 57gPPG (PPG molecular weight is 2000g/mol) are put into reactor,
80 DEG C, dehydration mixing 1h under 30Pa pressure, after octoate catalyst stannous 0.5g is added under inert gas protection, system starts to rise
Temperature is warming up to 120 DEG C of reaction 1h, then is warming up to 140 DEG C of reaction 1h, finally in 160 DEG C of reaction 2h, then in the case where pressure is 10Pa
Devolatilization 1h obtains white solid after discharging is cooling.44.5 DEG C of fusing point.
Embodiment 3
1000g caprolactone, 50g lactide and 122gPEG (PEG molecular weight is 5000g/mol) are put into reactor,
90 DEG C, dehydration mixing 1h under 10Pa pressure, after octoate catalyst stannous 0.5g is added under inert gas protection, system starts to rise
Temperature is warming up to 120 DEG C of reaction 1h, then is warming up to 140 DEG C of reaction 1h, finally in 160 DEG C of reaction 3h, then in the case where pressure is 10Pa
Devolatilization 1h obtains white solid after discharging is cooling.50.3 DEG C of fusing point.
Embodiment 4
1000g caprolactone, 200g lactide and 140gPPG (PPG molecular weight is 5000g/mol) are put into reactor,
Under 90 DEG C, 10Pa pressure dehydration mixing 1h, after catalyst dibutyltin dilaurylate 0.8g is added under inert gas protection,
System starts to warm up, and is warming up to 120 DEG C of reaction 1h, then is warming up to 140 DEG C of reaction 1h, finally in 160 DEG C of reaction 3h, is then pressing
Power is devolatilization 1h under 10Pa, obtains white solid after discharging is cooling.Test product acid value 0.2mgKOH/g, hydroxyl value, molecular weight
50000g/mol, 45.8 DEG C of fusing point.
Embodiment 5
By 1000g caprolactone, 100g2,2- dimethyltrimethylene carbonate and 73gPTMG, (PTMG molecular weight is
3000g/mol) put into reactor in, under 100 DEG C, 10Pa pressure dehydration mixing 1h, after under inert gas protection be added urge
Agent stannous octoate 1.0g, system start to warm up, and are warming up to 120 DEG C of reaction 1h, then are warming up to 140 DEG C of reaction 1h, finally 160
DEG C reaction 3h, then the devolatilization 1h in the case where pressure is 10Pa, obtains white solid after discharging is cooling.40.1 DEG C of fusing point.
Embodiment 6
1000g caprolactone, 40g trimethylene carbonate and 69gPTMG (PTMG molecular weight is 3000g/mol) investment is anti-
Answer in device, under 100 DEG C, 10Pa pressure dehydration mixing 1h, after octoate catalyst stannous 0.3g is added under inert gas protection,
System starts to warm up, and is warming up to 120 DEG C of reaction 1h, then is warming up to 140 DEG C of reaction 1h, finally in 160 DEG C of reaction 2h, is then pressing
Power is devolatilization 1h under 10Pa, obtains white solid after discharging is cooling.43.6 DEG C of fusing point.
Embodiment 7
1000g caprolactone, 50g trimethylene carbonate and 69gPTMG (PTMG molecular weight is 3000g/mol) investment is anti-
Answer in device, under 100 DEG C, 10Pa pressure dehydration mixing 1h, after catalyst n-heterocycle carbine is added under inert gas protection
0.3g, system start to warm up, and are warming up to 120 DEG C of reaction 1h, then are warming up to 140 DEG C of reaction 1h, finally in 160 DEG C of reaction 2h, so
The devolatilization 1h in the case where pressure is 10Pa afterwards, obtains white solid after discharging is cooling.43.6 DEG C of fusing point.
Comparative example
1000g caprolactone, 200gPEG (PEG molecular weight is 8000g/mol) are put into reactor, in 100 DEG C, 50Pa
Under pressure dehydration mixing 1h, after octoate catalyst stannous 0.72g is added under inert gas protection, system starts to warm up, heating
To 120 DEG C of reaction 1h, then 140 DEG C of reaction 1h are warming up to, finally in 160 DEG C of reaction 4h, the then devolatilization 1h in the case where pressure is 10Pa,
White solid is obtained after discharging is cooling.61.3 DEG C of fusing point.
Table 1 is product test result table.
Claims (5)
1. a kind of low temperature polycaprolactone preparation method that fusing point is controllable, it is reacted by weight by following raw materials:
1000 parts of caprolactone, 0.2-200 parts of modified monomer, initiator, 50-400 parts, 0.2-1.5 parts of catalyst, it is described modified single
Body includes at least one of glycolide, lactide, carbonic ester；The initiator includes polyethylene glycol, polypropylene glycol, poly- tetrahydro
At least one of furans；The catalyst is dibutyl tin dilaurate, stannous octoate, dilaurate dioctyl tin, three fourths
One of base phosphine, dimethylphenylphosphine, N- heterocycle carbine compound.
2. a kind of controllable low temperature polycaprolactone preparation method of fusing point according to claims 1 and 2, which is characterized in that institute
Stating initiator molecule amount is 2000-8000g/mol.
3. a kind of controllable low temperature polycaprolactone preparation method of fusing point according to claim 1, which is characterized in that before reaction
Raw material are carried out first at 80-100 DEG C, pressure 10-50Pa to be dehydrated preceding processing, and are uniformly mixed mixing.
4. a kind of controllable low temperature polycaprolactone preparation method of fusing point according to claim 1,2 or 3, which is characterized in that
Temperature-rise period is when reaction: 120 DEG C of reactions 1h, 140 DEG C of reactions 1h, 160 DEG C of reaction 2-4h, reaction under inert gas protection into
Row.
5. a kind of controllable low temperature polycaprolactone preparation method of fusing point according to claim 4, which is characterized in that reacted
In vacuum degree lower than devolatilization 1h under 20Pa after.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563569A (en) * | 2021-06-03 | 2021-10-29 | 深圳光华伟业股份有限公司 | Biodegradable polyester material with low melting point and preparation method and application thereof |
| CN114456555A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Low-VOC-content polycaprolactone resin and preparation method thereof |
| CN115323616A (en) * | 2022-08-16 | 2022-11-11 | 青岛大学 | Polycaprolactone superfine fiber two-dimensional porous membrane and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456555A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Low-VOC-content polycaprolactone resin and preparation method thereof |
| CN113563569A (en) * | 2021-06-03 | 2021-10-29 | 深圳光华伟业股份有限公司 | Biodegradable polyester material with low melting point and preparation method and application thereof |
| CN115323616A (en) * | 2022-08-16 | 2022-11-11 | 青岛大学 | Polycaprolactone superfine fiber two-dimensional porous membrane and preparation method thereof |
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Application publication date: 20190528 |