CN105949449A - Composite catalyst for preparing polyether-polylactide-aliphatic polycarbonate ternary block copolymer and application of composite catalyst - Google Patents
Composite catalyst for preparing polyether-polylactide-aliphatic polycarbonate ternary block copolymer and application of composite catalyst Download PDFInfo
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- 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
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Abstract
The invention relates to a composite catalyst for preparing a polyether-polylactide-aliphatic polycarbonate ternary block copolymer and an application of the composite catalyst. The composite catalyst comprises a metal Salen catalyst and a cocatalyst in a molar ratio of 1: (0.5-2), wherein the cocatalyst is bis-(triphenylphosphine)iminium chloride, 4-dimethylaminopyridine or 2,6-lutidine. The composite catalyst has the following beneficial effects: 1, The catalysis effect of the composite catalyst is good, the catalysis efficiency is high, the obtained ternary copolymer has larger number-average molecular weight and narrow molecular weight distribution; 2, composition of a polyether segment, a polylactide segment and a PPC (poly(propylene carbonate)) segment in the copolymer can be effectively controlled through regulation of step reaction time and monomer ratio, the glass transition temperature of the copolymer is 2-42 DEG C, the elongation at break is 55%-331%, and the tensile strength is 6-39 MPa.
Description
Technical field
The present invention relates to technical field of macromolecules, be particularly used for preparing polyethers-polylactide-fatty poly-ester carbonate
The composite catalyst of ternary block polymer and application thereof.
Background technology
Carbon dioxide is considered as the predominant gas causing " greenhouse effect ", result in global warming, Melting Glaciers and pole
The end climate change such as weather, therefore, utilizes and fixes carbon dioxide and arouse great concern.Solve the one of this problem
The approach of kind is that this abundant cheap CO_2 Resource is become polymeric articles.Since 1969, aboveground auspicious equality people
Initiative work, utilize carbon dioxide and epoxide synthctic fat adoption carbonic ester, become a kind of potential effective profit
With the important channel of carbon dioxide.The titanium dioxide with high alternating structure can be synthesized with carbon dioxide and expoxy propane for raw material
Carbon copolymer (polypropylene carbonate PPC), owing to main chain exists ester bond, this polymer is possible not only to light degradation, or a kind of complete
Biodegradable plastic, but there is glass transition temperature low (35 DEG C), heat decomposition temperature low (170 DEG C), degradation time length etc. in it
Defect.Many institutes are well-known, and polylactic acid (PLA), polyglycolic acid and polylactic acid are that a few is by the U.S. with the copolymer of polyglycolic acid
What food and drug administration was approved can be with the macromolecular material of Clinical practice in medical field.It is defeated that they are widely used in medicine
Send and human tissue engineering support field.PLA shows as the polymer of four kinds of different shapes, and wherein, having optically active has
PLLA and PDLA of the vertical structure of rule is hypocrystalline material, has higher fusing point (170 DEG C), higher mechanical strength, is usually used in system
Make operation suture thread, nail and orthopaedic devices etc..Poly-dl-lactide PDLLA is amorphous material, and medicine is at the single-phase base of PDLLA
Matter is prone to be uniformly distributed, is therefore usually used in controlled release drug delivery system.PDLA and PLLA carries out the compound solid that can be formed and answers
Compound, its fusing point is compared PLLA or PDLA and is significantly improved (up to 230 DEG C).But, when polylactic acid is as materials'use
Fragility compared with big, impact resistance is poor, and vivo degradation product is acidity, is easily caused some patients generation non-infectious inflammation etc.
And make it apply by a definite limitation.Introducing PLA segment in PPC main chain and be expected to the advantage of both combinations, preparation has good
Biological degradability, biocompatibility, hot property, the new type biodegradable plastics of mechanical property.
There are two blocks or multi-block polymer that three kinds of methods can synthesize PPC at present.One of which method is to add simultaneously
Enter various of monomer, utilize the selective polymerisation of catalyst monomer, random or block ter-polymers can be prepared.Such as Kroger
Et al. use acid imide zinc salt catalyst to achieve the terpolymerization of carbon dioxide, 7-oxa-bicyclo[4.1.0 and lactide, synthesize
Random or block polycyclic hexyl carbonate-polylactide.Can along with reaction the minimizing carrying out monomer concentration, the composition of segment with
Change.Therefore the method is difficult to the chain structure to polymer and molecular weight is controlled effectively.Another kind of method is with end
Hydroxyl PPC, as Macromolecular chain transfer agent, prepares block polymer.SalenCoX catalyst is first used such as Darensbourg et al.
Catalysis expoxy propane and the dualistic polymerization of carbon dioxide, with water as chain-transferring agent, be prepared for terminal hydroxy group fatty poly-ester carbonate,
Being subsequently adding catalyst 1,8-diazabicyclo [5,4,0]-ten one carbon-7-alkene (DBU) and lactide monomer, polylactide is from poly-
Increase at the hydroxyl at carbonic ester two ends, be prepared for polylactide-Merlon-polylactide ternary block polymer.The method
The chain structure of polymer and molecular weight effectively can be controlled, it may be desired to add chain-transferring agent and two kinds of catalyst, make shadow
The factor of sound increases.The third method is that the polymerization using active catalyst to be catalyzed the first monomer prepares active copolymer, then
Add the second monomer, continue to cause the polymerization of the second monomer to prepare block copolymer.As Coates et al. uses activity acyl
Imines zinc catalyst, the method being added various epoxide by substep is prepared for the polymerization of multiple block polycyclic hexamethylene carbonic ester
Thing.The segmented structure of this polymer and molecular weight effectively can be controlled by controlling stepwise reaction time and monomer ratio
System, for a kind of method preferably preparing block copolymer.Metalloporphyrin and metal salen catalyst are that a kind of structure determines, has
There is good modifiable catalyst, can apply to the active terpolymerization of carbon dioxide, expoxy propane and lactide, but
The method utilizing substep to add monomer is prepared polyethers-polylactide-polycarbonate block copolymer and be yet there are no document report,
Summary of the invention
The technical problem to be solved is for above-mentioned deficiency present in prior art, it is provided that one is used for making
The composite catalyst of standby polyethers-polylactide-fatty poly-ester carbonate ternary block polymer, utilizes this catalyst by substep
Addition expoxy propane, lactide, the method polymerization of carbon dioxide monomer obtain polyethers-polylactide-fatty poly-ester carbonate three
Unit's block copolymer.
For solving above-mentioned technical problem, present invention provide the technical scheme that a kind of for prepare polyethers-polylactide-
The composite catalyst of fatty poly-ester carbonate ternary block polymer, it is characterised in that described composite catalyst is by metal salung
(SalenM, M=Cr, Co) catalyst forms with promoter, and metal salen catalyst is 1 with the mol ratio of promoter:
0.5-2, wherein the structural formula of metal salen catalyst is:
M=Cr or Co；R1=-C6H4-(ortho position di-substituted-phenyl), 1,2-cyclohexyl ,-CH2CH2-or-CH (CH3)CH2-；
R2=CH3、t-Bu；R3=Br, CH3, t-Bu or CH2Cl；X is-Cl, CF3COO-, 2,4-DNP epoxide or 2,4,6-tri-
Nitrophenol epoxide；
Described promoter is double-(dihalotriphenylphosphoranes base) ammonium chloride, DMAP or 2,6-lutidines.
A kind of composite catalyst for preparing polyethers-polylactide-fatty poly-ester carbonate ternary block polymer, its
Being characterised by, described composite catalyst is made up of with promoter catalysis of metalloporphyrin agent, metalloporphyrin (PorphyrinM, M=
Cr, Co, Al) mol ratio of catalyst and promoter is 1:0.5-2, wherein the structural formula of catalysis of metalloporphyrin agent is:
M=Cr, Co or Al；R2=H, Br, F or-OMe；R3And R4For F or H；X is-Cl ,-OEt, CCl3COO-or 2,4-
Dinitrophenol,DNP epoxide；
Described promoter is double-(dihalotriphenylphosphoranes base) ammonium chloride, DMAP or 2,6-lutidines.
Novel polyether-polylactide-fatty poly-ester carbonate ternary block polymer prepared by catalyst described in utilization
Method, it is characterised in that: by metal salen catalyst or catalysis of metalloporphyrin agent and promoter, that expoxy propane adds high pressure is anti-
Answer in still, react 0.5-24 hour, add lactide, 1-6 hour response time, in autoclave, be full of rapidly titanium dioxide
In carbon makes still, pressure maintains 1.0-5.0MPa, polyreaction, and polyreaction adds a large amount of hydrochloric acid methanol (HCl mass after terminating
Percentage concentration is 1%) solution termination reaction, products therefrom a large amount of methanol washing obtains novel polyether-polylactide-aliphatic
Merlon ternary block polymer.
By such scheme, described lactide is dissolved in expoxy propane or appropriate solvent, lactide and expoxy propane or molten
The mol ratio of agent is 1:5-10；Described solvent is dichloromethane, toluene or dioxane.
By the mol ratio of such scheme, metal salen catalyst or catalysis of metalloporphyrin agent Yu promoter be 1:0.5-2,
The mol ratio of metal salen catalyst or catalysis of metalloporphyrin agent and expoxy propane is 1:100-5000.
It is 1:1-50 by the mol ratio of such scheme, lactide and expoxy propane.
By such scheme, polymeric reaction temperature is 25-100 DEG C, and the response time is 15-48 hour.
The present invention under catalysis of metalloporphyrin agent or metal salen catalyst catalytic action, expoxy propane, lactide and two
Carbonoxide carries out block copolymerization by anionic coordinate polymerization, and promoter is coordinated in catalyst center, promotes the key entry of monomer.
Polyethers-polylactide-fatty poly-ester carbonate the ternary block polymer prepared according to said method, described
Terpolymer number-average molecular weight is 10000-25500, and molecular weight distribution is 1.1-1.5, and in copolymer, polyethers PPO segment rubs
Your percentage composition is 3-23%, and the molar content of polylactide PLA segment is 11-70%, rubbing of Merlon PPC segment
Your percentage composition is 18-69%, and the glass transition temperature of copolymer is 2-42 DEG C, and (test condition, under nitrogen atmosphere, heat up speed
Rate is 10 DEG C/min, temperature elevating range-30 DEG C to 200 DEG C), elongation at break is 55-331%, and hot strength is that 6-39MPa (presses
ASTM-D638 standard method, less than vitrification point 15 DEG C test, rate of extension 50mm/min).
The beneficial effects of the present invention is: 1, composite catalyst catalytic effect used by the present invention is good, can be catalyzed ring step by step
The polymerization of Ethylene Oxide, the polymerization of lactide and carbon dioxide and the combined polymerization of expoxy propane, catalytic efficiency is high, and gained ternary is altogether
Polymers number-average molecular weight relatively big (Mn is 10000-25500), narrow molecular weight distribution (PDI is less than 1.5).2, polyether chain in copolymer
Section, the composition of polylactide segment, PPC segment effectively can control by adjusting stepwise reaction time and monomer ratio,
The molar content of PPO segment is 3-23%, and the molar content of polylactide PLA segment is 11-70%, Merlon
The molar content of PPC segment is 18-69%.3, polyethers-polylactide-fatty poly-ester carbonate ternary prepared by the present invention
Block copolymer has regulatable hot property and mechanical property in wider scope: the glass transition temperature of copolymer is
2-42 DEG C, elongation at break is 55-331%, and hot strength is 6-39MPa.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum of the polymer prepared by the embodiment of the present invention 11H NMR schemes；
Fig. 2 is the nuclear-magnetism carbon spectrum of the polymer prepared by embodiment 113C NMR schemes；
Fig. 3 is the DSC figure contrast of the polymer prepared by embodiment 2 and 7 and PPC and PLA.
Detailed description of the invention
For making those skilled in the art be more fully understood that technical scheme, below in conjunction with example the present invention made into
One step describes in detail.
Embodiment 1
By SalenCrCl catalyst 22.7mg (0.036mmol) as shown in above formula, promoter DMAP 8.78mg
(0.072mmol) (SalenCrCl catalyst: promoter: epoxy it is separately added in autoclave with expoxy propane 0.5mL
Propane=1:2:200 (mol ratio)), polymeric reaction temperature is 60 DEG C, after reacting 12 hours, adds lactide 1.037g (third
The mol ratio of lactide and expoxy propane is 1:1) and solvent dioxane 5mL, after reacting 2 hours more logical in autoclave
Entering pressure in carbon dioxide makes still and maintain 3MPa, the response time is 18 hours, and reaction adds 100mL hydrochloric acid methanol after terminating
(HCl mass percentage concentration is 1%) terminates reaction, and products therefrom wash with a large amount of methanol, and vacuum drying obtains white polyethers-gather
Lactide-fatty poly-ester carbonate ternary block polymer 1.6g, its number-average molecular weight is 10000, and molecular weight distribution is 1.25.
Polymer prepared by the present embodiment1H NMR spectra is as it is shown in figure 1, be polyester in polymer at 5.15ppm in figure
PLA segment (-CH (CH3) COO-) peak of methine hydrogen in unit, at 5.0ppm be Merlon PPC segment in polymer (-
CH2CH(CH3) OCOO-) and in the peak of methine hydrogen, be Merlon PPC segment (-CH in polymer at 4.2ppm2CH(CH3)
OCOO-) peak of methylene hydrogen, is polyethers PPO segment (-OCH (CH in polymer at 3.5ppm3)CH2-) in methine and Asia
The peak of methyl, it is seen that polymer formulae is (-OCH (CH3)CH2-)a(-CH(CH3)COO-)b(-CH2CH(CH3)OCOO)c-H,
The molar content PPC%=A of fatty poly-ester carbonate PPC segment5.0/(A5.0+A5.1+A3.5/3).Prepared by the present embodiment
Polymer13C NMR spectra as in figure 2 it is shown, in figure the peak at 169.5ppm be polyester PLA segment (-CH (CH in polymer3)
COO-) peak of ester group-COO-carbon in unit, is Merlon PPC segment (-CH in polymer at 154.6ppm2CH(CH3)
OCOO-) peak of carbonate group-OCOO-carbon in unit, is polyethers PPO segment (-OCH (CH in polymer at 74.1ppm3)CH2-)
The peak of-OCH-carbon in unit, the molar content PPC%=A of fatty poly-ester carbonate PPC segment154.6/(A169.5+A154.6+
A74.1), by polymer1H H NMR spectroscopy or13C H NMR spectroscopy calculates and all can obtain moles hundred of PPC segment in terpolymer
Dividing content to be about 23%, the molar content of PPO segment is about 14%, and the molar content of PLA segment is about 63%, altogether
The glass transition temperature of polymers is 40 DEG C, and elongation at break is 68%, and hot strength is 35MPa.
Embodiment 2
By the SalenCo (OC as shown in above formula6H3(NO2)2) catalyst 29mg (0.035mmol), promoter 2,6-bis-
Picoline 7.58mg (0.07mmol) and expoxy propane 12.2mL (175mmol) is separately added into (mol ratio in autoclave
SalenCo(OC6H3(NO2)2) catalyst: promoter: expoxy propane=1:2:5000), polymeric reaction temperature is 25 DEG C, instead
After answering 24 hours, add lactide 2.52g (mol ratio of lactide and expoxy propane is 1:10) and methylene chloride
10mL, after reacting 6 hours, then is filled with carbon dioxide rapidly in autoclave, and in still, pressure maintains 1.5MPa, during reaction
Between be 22 hours, reaction terminate after add 100mL hydrochloric acid methanol (HCl mass percentage concentration is 1%) terminate reaction, products therefrom
Washing with a large amount of methanol, vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer
3.3g, its number-average molecular weight is 14350, and molecular weight distribution is 1.25, and in copolymer, the molar content of PPO segment is 9%,
The molar content of PLA segment is 70%, and the molar content of PPC segment is 21%, the glass transition temperature of copolymer
Degree is 42 DEG C, and elongation at break is 55%, and hot strength is 39MPa.
Embodiment 3
By the SalenCr (OOCCF as shown in above formula3) catalyst 23mg (0.035mmol), double-(dihalotriphenylphosphoranes base)
Ammonium chloride PPNCl 10mg (0.0175mmol) and expoxy propane 12.2mL (175mmol) are separately added in autoclave and (rub
You are than SalenCr (OOCCF3) catalyst: promoter: expoxy propane=1:0.5:5000), polymeric reaction temperature is 60 DEG C,
After reacting 10 hours, add the expoxy propane 5mL of lactide 0.504g (mol ratio of lactide and expoxy propane is 1:50)
Solution, after reacting 6 hours, then is filled with carbon dioxide rapidly in autoclave, and in still, pressure maintains 4.5MPa, during reaction
Between be 22 hours, reaction terminate after add 100mL hydrochloric acid methanol (HCl mass percentage concentration is 1%) terminate reaction, products therefrom
Washing with a large amount of methanol, vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer
0.6g, its number-average molecular weight is 11000, and molecular weight distribution is 1.35, and in copolymer, the molar content of PPO segment is
The molar content of 10%, PLA segment is 54%, and the molar content of PPC segment is 36%, and the vitrification of copolymer turns
Temperature is 39 DEG C, and elongation at break is 73%, and hot strength is 33MPa.
Embodiment 4
By the SalenCr (OC as shown in above formula6H2(NO2)3) catalyst 21mg (0.035mmol), promoter
PPNCl40mg (0.07mmol) and expoxy propane 12.2mL (175mmol), is separately added into (mol ratio in autoclave
SalenCr(OC6H2(NO2)3) catalyst: promoter: expoxy propane=1:2:5000), polymeric reaction temperature is 60 DEG C, instead
After answering 18 hours, add the expoxy propane 12.5mL of lactide 2.52g (mol ratio of lactide and expoxy propane is 1:50)
Solution, after reacting 1 hour, then in autoclave, be filled with carbon dioxide rapidly, in still, pressure maintains 3.5MPa, reaction
Time is 22 hours, and reaction adds 100mL hydrochloric acid methanol (HCl mass percentage concentration is 1%) after terminating and terminates reaction, gained
Product washs with a large amount of methanol, and vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer
3g, its number-average molecular weight is 17000, and molecular weight distribution is 1.3, and in copolymer, the molar content of PPO segment is 13%,
The molar content of PLA segment is 35%, and the molar content of PPC segment is 52%, the glass transition temperature of copolymer
Degree is 35 DEG C, and elongation at break is 153%, and hot strength is 23MPa.
Embodiment 5
By porphyrin aluminum PorphyrinAl (OEt) catalyst 23.9mg (0.035mmol) as shown in above formula, promoter
PPNCl20mg (0.035mmol) and expoxy propane 12.2mL (175mmol), is separately added in autoclave (mol ratio porphyrin
Aluminum PorphyrinAl (OEt) catalyst: promoter: expoxy propane=1:1:5000), polymeric reaction temperature is 60 DEG C, reaction
After 8 hours, add the dichloromethane 10mL solution of lactide 2.52g (mol ratio of lactide and expoxy propane is 1:10),
After reacting 1 hour, then being filled with carbon dioxide to autoclave rapidly, in still, pressure maintains 3.5MPa, and the response time is 22
Hour, reaction adds 100mL methanol hydrochloride solution (HCl mass percentage concentration is 1%) after terminating and terminates reaction, and products therefrom is used
A large amount of methanol washings, vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer 3.2g,
Its number-average molecular weight is 18700, and molecular weight distribution is 1.43, and in copolymer, the molar content of PPO segment is 3%, PLA chain
The molar content of section is 28%, and the molar content of PPC segment is 69%, and the glass transition temperature of copolymer is 35
DEG C, elongation at break is 194%, and hot strength is 21MPa.
Embodiment 6
By the PorphyrinAl (O (C as shown in above formula6H3(NO2)2) catalyst 26.6mg (0.035mmol), co-catalysis
Agent DMAP 4.27mg (0.035mmol) and expoxy propane 12.2mL, be separately added into (mol ratio in autoclave
PorphyrinAl(O(C6H3(NO2)2) catalyst: promoter: expoxy propane=1:1:5000), polymeric reaction temperature is 25
DEG C, after reacting 24 hours, add the expoxy propane of lactide 5.04g (mol ratio of lactide and expoxy propane is 1:5)
12.5mL solution, after reacting 2 hours, then is filled with carbon dioxide rapidly in still, and in still, pressure maintains 3.5MPa, response time
Being 48 hours, reaction adds 100mL methanol hydrochloride solution (HCl weight/mass percentage composition is 1%) after terminating and terminates reaction, and gained produces
Thing washs with a large amount of methanol, and vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer
5.5g, its number-average molecular weight is 25500, and molecular weight distribution is 1.5, and in copolymer, the molar content of PPO segment is 15%,
The molar content of PLA segment is 67%, and the molar content of PPC segment is 18%, the glass transition temperature of copolymer
Degree is 39 DEG C, and elongation at break is 97%, and hot strength is 30MPa.
Embodiment 7
By PorphyrinCrCl catalyst 37.6mg (0.035mmol) as shown in above formula, promoter 2,6-dimethyl
Pyridine 7.5g (0.07mmol) and expoxy propane 12.2mL, is separately added in 100mL autoclave that (PorphyrinCrCl urges
Agent: promoter: lactide: expoxy propane=1:2:500:5000 (mol ratio)), polymeric reaction temperature is 60 DEG C, reaction
After 30min, add the dioxane 10mL solution of lactide 2.52g (mol ratio of lactide and expoxy propane is 1:10),
After reacting 1 hour, then being filled with carbon dioxide in autoclave rapidly, in still, pressure maintains 1MPa, and the response time is 15
Hour, reaction adds 100mL methanol hydrochloride solution (HCl mass percentage concentration is 1%) after terminating and terminates reaction, and products therefrom is used
A large amount of methanol washings, vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer 2.8g,
Its number-average molecular weight is 14600, and molecular weight distribution is 1.5, and in copolymer, the molar content of PPO segment is 23%, PLA chain
The molar content of section is 11%, and the molar content of PPC segment is 66%, and the glass transition temperature of copolymer is 2
DEG C, elongation at break is 331%, and hot strength is 6MPa.
Embodiment 8
By PorphyrinCoCl catalyst 37.3mg (0.035mmol) as shown in above formula, promoter PPNCl 20mg
(0.035mmol) being separately added in autoclave with expoxy propane 0.98mL (14mmol), mol ratio PorphyrinCoCl is urged
Agent: promoter: expoxy propane=1:1:400, polymeric reaction temperature is 100 DEG C, after reacting 4 hours, adds lactide
The dioxane 10mL solution of 2.016g (mol ratio of lactide and expoxy propane is 1:1), after reacting 6 hours, more rapidly to
Being filled with carbon dioxide in autoclave, in still, pressure maintains 3.5MPa, and the response time is 22 hours, and reaction adds after terminating
100mL hydrochloric acid methanol terminates reaction, and products therefrom washs with a large amount of methanol, and vacuum drying obtains white polyethers-polylactide-fat
Fat adoption carbonic ester ternary block polymer 2.1g, its number-average molecular weight is 10000, and molecular weight distribution is 1.25, in copolymer
The molar content of PPO segment is 10%, and the molar content of PLA segment is 27%, the molar content of PPC segment
Being 63%, the glass transition temperature of copolymer is 33 DEG C, and elongation at break is 205%, and hot strength is 18MPa.
Embodiment 9
By the PorphyrinAl (OOCCCl as shown in above formula3) catalyst 39mg (0.035mmol), promoter PPNCl
20mg (0.035mmol) and expoxy propane 12.2mL (175mmol) is separately added into (PorphyrinAl in autoclave
(OOCCCl3) catalyst: PPNCl: expoxy propane=1:1:5000 (mol ratio)), polymeric reaction temperature is 60 DEG C, and reaction 20 is little
Shi Hou, adds the dioxane 10mL solution of lactide 2.52g (mol ratio of lactide and expoxy propane is 1:10), instead
After answering 1 hour, then being filled with carbon dioxide in autoclave rapidly, in still, pressure maintains 3.5MPa, and the response time is 22
Hour, reaction adds hydrochloric acid methanol after terminating and terminates reaction, and products therefrom washs with a large amount of methanol, obtains white polyethers-poly-third
Lactide-fatty poly-ester carbonate ternary block polymer 3.2g, its number-average molecular weight is 14000, and molecular weight distribution is 1.1, altogether
In polymers, the molar content of PPO segment is 14%, and the molar content of PLA segment is 31%, moles the hundred of PPC segment
Dividing content is 55%, and the glass transition temperature of copolymer is 35 DEG C, and elongation at break is 187%, and hot strength is 20MPa.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out
Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (7)
1., for preparing a composite catalyst for polyethers-polylactide-fatty poly-ester carbonate ternary block polymer, it is special
Levying and be, described composite catalyst is made up of with promoter metal salen catalyst, metal salen catalyst and promoter
Mol ratio be 1:0.5-2, wherein the structural formula of metal salen catalyst is:
M=Cr or Co；R1=-C6H4-(ortho position di-substituted-phenyl), 1,2-cyclohexyl ,-CH2CH2-or-CH (CH3)CH2-；R2=
CH3、t-Bu；R3=Br, CH3, t-Bu or CH2Cl；X is-Cl, CF3COO-, 2,4-DNP epoxide or 2,4,6-trinitro-s
Phenol epoxide；
Described promoter is double-(dihalotriphenylphosphoranes base) ammonium chloride, DMAP or 2,6-lutidines.
2., for preparing a composite catalyst for polyethers-polylactide-fatty poly-ester carbonate ternary block polymer, it is special
Levying and be, described composite catalyst is made up of with promoter catalysis of metalloporphyrin agent, catalysis of metalloporphyrin agent and promoter
Mol ratio be 1:0.5-2, wherein the structural formula of catalysis of metalloporphyrin agent is:
M=Cr, Co or Al；R2=H, Br, F or-OMe；R3And R4For F or H；X is-Cl ,-OEt, CCl3COO-or 2,4-dinitro
Phenol epoxide；
Described promoter is double-(dihalotriphenylphosphoranes base) ammonium chloride, DMAP or 2,6-lutidines.
3. one kind utilizes the catalyst described in claim 1 or 2 to prepare novel polyether-polylactide-fatty poly-ester carbonate three
The method of unit's block copolymer, it is characterised in that: by metal salen catalyst or catalysis of metalloporphyrin agent and promoter, epoxy
Propane adds in autoclave, reacts 0.5-24 hour, adds lactide, and 1-6 hour response time, rapidly to reaction under high pressure
Being full of pressure in carbon dioxide makes still in still and maintain 1.0-5.0MPa, polyreaction, polyreaction adds a large amount of salt after terminating
Acid methanol solution terminates reaction, and products therefrom a large amount of methanol washing obtains novel polyether-polylactide-fatty poly-ester carbonate
Ternary block polymer.
Method the most according to claim 3, it is characterised in that described lactide is dissolved in expoxy propane or appropriate solvent,
Lactide is 1:5-10 with the mol ratio of expoxy propane or solvent；Described solvent is dichloromethane, toluene or dioxane.
Method the most according to claim 3, it is characterised in that metal salen catalyst or catalysis of metalloporphyrin agent are urged with helping
The mol ratio of agent is 1:0.5-2, metal salen catalyst or catalysis of metalloporphyrin agent are 1 with the mol ratio of expoxy propane:
100-5000。
Method the most according to claim 3, it is characterised in that the mol ratio of lactide and expoxy propane is 1:1-50.
Method the most according to claim 3, it is characterised in that polymeric reaction temperature is 25-100 DEG C, the response time is 15-
48 hours.
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