CN105949449B - It is used to prepare polyethers-polylactide-fatty poly-ester carbonate ternary block polymer composite catalyst and its application - Google Patents
It is used to prepare polyethers-polylactide-fatty poly-ester carbonate ternary block polymer composite catalyst and its application Download PDFInfo
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- 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
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- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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Abstract
The present invention relates to be used to prepare polyethers-polylactide-fatty poly-ester carbonate ternary block polymer composite catalyst and its application, the composite catalyst is made of metal salen catalyst with co-catalyst, the molar ratio of metal salen catalyst and co-catalyst is 1:0.5-2, the co-catalyst is double-(dihalotriphenylphosphoranes base) ammonium chloride, 4-dimethylaminopyridine or 2,6- lutidines.The beneficial effects of the present invention are: 1, present invention the used in composite catalyst catalytic effect good, and high catalytic efficiency, gained terpolymer number-average molecular weight is larger, narrow molecular weight distribution.2, polyether segment in copolymer, polylactide segment, PPC segment composition can effectively be controlled by adjusting stepwise reaction time and monomer ratio, the glass transition temperature of copolymer is 2-42 DEG C, elongation at break is 55-331%, tensile strength 6-39MPa.
Description
Technical field
The present invention relates to technical field of macromolecules, and in particular to is used to prepare polyethers-polylactide-fatty poly-ester carbonate
The composite catalyst of ternary block polymer and its application.
Background technique
Carbon dioxide is considered as the predominant gas for causing " greenhouse effects ", results in global warming, Melting Glacierss and pole
Hold the climate changes such as weather, therefore, using and fixed carbon dioxide arouse great concern.Solve the problems, such as this one
Kind approach is that this cheap CO_2 Resource abundant is become polymeric articles.Since 1969, Jing Shangxiang equality people
Start sex work, using carbon dioxide and epoxide synthctic fat adoption carbonic ester, become a kind of potential effectively benefit
With the important channel of carbon dioxide.The titanium dioxide with high alternating structure can be synthesized using carbon dioxide and propylene oxide as raw material
Carbon copolymer (polypropylene carbonate PPC), since main chain is there are ester bond, which not only can be complete with light degradation, or one kind
Biodegradable plastic, but that there are glass transition temperatures is low (35 DEG C) for it, and thermal decomposition temperature is low (170 DEG C), and degradation time is long etc.
Defect.Many institutes are well-known, and the copolymer of polylactic acid (PLA), polyglycolic acid and polylactic acid and polyglycolic acid is a few by the U.S.
Food and drug administration approve medical field can be with the high molecular material of clinical use.It is defeated that they are widely used in drug
It send and human tissue engineering support field.PLA shows as the polymer of four kinds of different shapes, wherein with optical activation to have
The PLLA and PDLA for advising vertical structure are half hitch eutectic substances, and fusing point (170 DEG C) with higher, higher mechanical strength is usually used in making
Make operation suture thread, bone nail and orthopaedic devices etc..Poly-dl-lactide PDLLA is amorphous material, and drug is in the single-phase base of PDLLA
It is easy to be uniformly distributed in matter, therefore is usually used in controlled release drug delivery system.PDLA and PLLA progress is compound can to form solid again
Object is closed, fusing point is significantly improved compared to PLLA or PDLA (up to 230 DEG C).But polylactic acid as materials'use when
Brittleness is larger, impact resistance is poor, and catabolite is easy to cause some patientss that non-infectious inflammation etc. occurs in acidity in vivo
And it is subject to certain restrictions its application.PLA segment is introduced in PPC main chain and is expected to the advantages of combining the two, and preparation has good
Biological degradability, biocompatibility, hot property, mechanical property new type biodegradable plastics.
There are three types of two blocks or multi-block polymer that method can synthesize PPC at present.One of method is to add simultaneously
Enter various of monomer, using the selective polymerisation of catalyst monomer, random or block ter-polymers can be prepared.Such as Kroger
Et al. the terpolymerization of carbon dioxide, 7-oxa-bicyclo[4.1.0 and lactide is realized using acid imide zinc salt catalyst, synthesis
Random or block polycyclic hexyl carbonate-polylactide.Can with the reduction of the progress monomer concentration of reaction, the composition of segment with
Change.Therefore this method is difficult to be controlled effectively to the chain structure and molecular weight of polymer.Another method is to hold
Hydroxyl PPC prepares block polymer as Macromolecular chain transfer agent.As Darensbourg et al. first uses SalenCoX catalyst
The dualistic polymerization of catalysis propylene oxide and carbon dioxide is prepared for terminal hydroxy group fatty poly-ester carbonate using water as chain-transferring agent,
Then it is added catalyst 1,-ten one carbon -7- alkene (DBU) of 8- diazabicyclo [5,4,0] and lactide monomer, polylactide is from poly-
Increase at the hydroxyl at carbonic ester both ends, is prepared for polylactide-polycarbonate-polylactide ternary block polymer.This method
Can chain structure to polymer and molecular weight effectively controlled, it may be desired to chain-transferring agent and two kinds of catalyst is added, makes shadow
The factor of sound increases.The third method is to be catalyzed the polymerization of the first monomer using active catalyst to prepare active copolymer, then
Second of monomer is added, the polymerization for continuing to cause second of monomer prepares block copolymer.As Coates et al. uses active acyl
Imines zinc catalyst is prepared for a variety of block polycyclic hexamethylene carbonic acid polyisocyanate polyadditions by the method that various epoxides are added step by step
Object.The segmented structure and molecular weight of the polymer can effectively be controlled by control stepwise reaction time and monomer ratio
System, for a kind of method for preferably preparing block copolymer.Metalloporphyrin and metal salen catalyst are a kind of structure determination, tool
There is good modifiable catalyst, can apply to the active terpolymerization of carbon dioxide, propylene oxide and lactide, but
Preparing polyethers-polylactide-polycarbonate block copolymer using the method that monomer is added in substep yet there are no document report,
Summary of the invention
It is a kind of for making the technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide
The composite catalyst of standby polyethers-polylactide-fatty poly-ester carbonate ternary block polymer passes through substep using the catalyst
Be added propylene oxide, lactide, carbon dioxide monomer method polymerize to obtain polyethers-polylactide-fatty poly-ester carbonate three
First block copolymer.
In order to solve the above technical problems, present invention provide the technical scheme that one kind is used to prepare polyethers-polylactide-
The composite catalyst of fatty poly-ester carbonate ternary block polymer, which is characterized in that the composite catalyst is by metal salung
(SalenM, M=Cr, Co) catalyst and co-catalyst form, and the molar ratio of metal salen catalyst and co-catalyst is 1:
0.5-2, the wherein structural formula of metal salen catalyst are as follows:
M=Cr or Co；R1=-C6H4(ortho position di-substituted-phenyl), 1,2- cyclohexyl ,-CH2CH2Or-CH (CH3)CH2-；
R2=CH3,t-Bu；R3=Br, CH3, t-Bu or CH2Cl；X is-Cl, CF3COO-, 2,4-DNP oxygroup or 2,4,6- tri-
Nitrophenol oxygroup；
The co-catalyst is double-(dihalotriphenylphosphoranes base) ammonium chloride, 4-dimethylaminopyridine or 2,6- lutidines.
It is a kind of to be used to prepare polyethers-polylactide-fatty poly-ester carbonate ternary block polymer composite catalyst,
It is characterized in that, the composite catalyst is made of catalysis of metalloporphyrin agent with co-catalyst, metalloporphyrin (PorphyrinM, M=
Cr, Co, Al) molar ratio of catalyst and co-catalyst is 1:0.5-2, the wherein structural formula of catalysis of metalloporphyrin agent are as follows:
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 oxygroup；
The co-catalyst is double-(dihalotriphenylphosphoranes base) ammonium chloride, 4-dimethylaminopyridine or 2,6- lutidines.
Utilize the catalyst preparation novel polyether-polylactide-fatty poly-ester carbonate ternary block polymer
Method, it is characterised in that: metal salen catalyst or catalysis of metalloporphyrin agent and co-catalyst, propylene oxide addition high pressure is anti-
It answers in kettle, reacts 0.5-24 hours, lactide is added, reaction time 1-6 hour is full of rapidly titanium dioxide into autoclave
Carbon makes in kettle pressure maintain 1.0-5.0MPa, polymerization reaction, and a large amount of hydrochloric acid methanols (HCl mass is added after polymerization reaction
Percentage concentration is that 1%) solution terminates reaction, and products therefrom is washed to obtain novel polyether-polylactide-aliphatic with a large amount of methanol
Polycarbonate ternary block polymer.
According to the above scheme, the lactide is dissolved in propylene oxide or appropriate solvent, lactide and propylene oxide or molten
The molar ratio of agent is 1:5-10；The solvent is methylene chloride, toluene or dioxane.
According to the above scheme, the molar ratio of metal salen catalyst or catalysis of metalloporphyrin agent and co-catalyst be 1:0.5-2,
The molar ratio of metal salen catalyst or catalysis of metalloporphyrin agent and propylene oxide is 1:100-5000.
According to the above scheme, the molar ratio of lactide and propylene oxide is 1:1-50.
According to the above scheme, polymeric reaction temperature is 25-100 DEG C, and the reaction time is 15-48 hours.
The present invention is under catalysis of metalloporphyrin agent or metal salen catalyst catalytic action, propylene oxide, lactide and two
Carbonoxide carries out block copolymerization by anionic coordinate polymerization, and co-catalyst is coordinated in catalyst center, promotes the key entry of monomer.
Polyethers-polylactide-fatty poly-ester carbonate the ternary block polymer being prepared according to the above method, it is described
Terpolymer number-average molecular weight is 10000-25500, molecular weight distribution 1.1-1.5, and polyethers PPO segment rubs in copolymer
Your percentage composition is 3-23%, and the molar content of polylactide PLA segment is 11-70%, and polycarbonate PPC segment rubs
Your percentage composition is 18-69%, the glass transition temperature of copolymer be 2-42 DEG C (test condition, under nitrogen atmosphere, heating speed
Rate is 10 DEG C/min, -30 DEG C to 200 DEG C of temperature elevating range), elongation at break 55-331%, tensile strength is that 6-39MPa (is pressed
ASTM-D638 standard method, lower than 15 DEG C of glass transition temperature tests, rate of extension 50mm/min).
The beneficial effects of the present invention are: 1, present invention the used in composite catalyst catalytic effect good, can be catalyzed ring step by step
The polymerization of Ethylene Oxide, the polymerization of lactide and the combined polymerization of carbon dioxide and propylene oxide, high catalytic efficiency, gained ternary are total
Polymers number-average molecular weight larger (Mn 10000-25500), narrow molecular weight distribution (PDI is less than 1.5).2, polyether chain in copolymer
Section, polylactide segment, PPC segment composition can effectively be controlled 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%, polycarbonate
The molar content of PPC segment is 18-69%.3, polyethers-polylactide-fatty poly-ester carbonate ternary prepared by the present invention
Block copolymer is with regulatable hot property and mechanical property in a wider scope: the glass transition temperature of copolymer is
2-42 DEG C, elongation at break 55-331%, tensile strength 6-39MPa.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum of polymer prepared by the embodiment of the present invention 11H NMR figure；
Fig. 2 is the nuclear-magnetism carbon spectrum of polymer prepared by embodiment 113C NMR figure；
Fig. 3 is polymer prepared by embodiment 2 and 7 and the DSC figure comparison of PPC and PLA.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, below with reference to example to the present invention make into
One step detailed description.
Embodiment 1
The SalenCrCl catalyst 22.7mg (0.036mmol) as shown in above formula, co-catalyst DMAP 8.78mg
(0.072mmol) and propylene oxide 0.5mL are separately added into autoclave (SalenCrCl catalyst: co-catalyst: epoxy
Propane=1:2:200 (molar ratio)), polymeric reaction temperature is 60 DEG C, after reaction 12 hours, adds lactide 1.037g (third
The molar ratio of lactide and propylene oxide is 1:1) and solvent dioxane 5mL, after reaction 2 hours, then into autoclave it is logical
Entering carbon dioxide makes pressure in kettle maintain 3MPa, and the reaction time is 18 hours, and 100mL hydrochloric acid methanol is added after reaction
(HCl mass percentage concentration is 1%) terminates reaction, and products therefrom is washed with a large amount of methanol, and it is poly- that vacuum drying obtains white polyethers-
Lactide-fatty poly-ester carbonate ternary block polymer 1.6g, number-average molecular weight 10000, molecular weight distribution 1.25.
Polymer prepared by the present embodiment1H NMR spectra is as 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 for polycarbonate PPC segment in polymer (-
CH2CH(CH3) OCOO-) and in methine hydrogen peak, be polycarbonate PPC segment (- CH in polymer at 4.2ppm2CH(CH3)
OCOO-) the 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 is as shown in Fig. 2, the peak in figure at 169.5ppm is polyester PLA segment (- CH (CH in polymer3)
COO-) in unit ester group-COO- carbon peak, be polycarbonate PPC segment (- CH in polymer at 154.6ppm2CH(CH3)
OCOO-) in unit carbonate group-OCOO- carbon peak, be 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), pass through polymer1H H NMR spectroscopy or13C H NMR spectroscopy calculates moles hundred of PPC segment in available terpolymer
It is about the molar content of 14%, PLA segment is about 63% that point content, which is about the molar content of 23%, PPO segment, altogether
The glass transition temperature of polymers is 40 DEG C, elongation at break 68%, tensile strength 35MPa.
Embodiment 2
SalenCo (the OC as shown in above formula6H3(NO2)2) catalyst 29mg (0.035mmol), co-catalyst 2,6- bis-
Picoline 7.58mg (0.07mmol) and propylene oxide 12.2mL (175mmol) are separately added into autoclave (molar ratio
SalenCo(OC6H3(NO2)2) catalyst: co-catalyst: propylene oxide=1:2:5000), polymeric reaction temperature is 25 DEG C, instead
After answering 24 hours, lactide 2.52g (molar ratio of lactide and propylene oxide is 1:10) and methylene chloride are added
10mL then is filled with rapidly carbon dioxide after reaction 6 hours into autoclave, and pressure maintains 1.5MPa in kettle, when reaction
Between be 22 hours, 100mL hydrochloric acid methanol (HCl mass percentage concentration be 1%) is added after reaction and terminates reaction, products therefrom
It is washed with a large amount of methanol, vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer
3.3g, number-average molecular weight 14350, molecular weight distribution 1.25, the molar content of PPO segment is 9% in copolymer,
The molar content of PLA segment is that the molar content of 70%, PPC segment is 21%, the glass transition temperature of copolymer
Degree is 42 DEG C, elongation at break 55%, tensile strength 39MPa.
Embodiment 3
SalenCr (the OOCCF as shown in above formula3) catalyst 23mg (0.035mmol), double-(dihalotriphenylphosphoranes base)
Ammonium chloride PPNCl 10mg (0.0175mmol) and propylene oxide 12.2mL (175mmol) are separately added into autoclave and (rub
You are than SalenCr (OOCCF3) catalyst: co-catalyst: propylene oxide=1:0.5:5000), polymeric reaction temperature is 60 DEG C,
After reaction 10 hours, the propylene oxide 5mL of lactide 0.504g (molar ratio of lactide and propylene oxide is 1:50) is added
Solution then is filled with rapidly carbon dioxide after reaction 6 hours into autoclave, and pressure maintains 4.5MPa in kettle, when reaction
Between be 22 hours, 100mL hydrochloric acid methanol (HCl mass percentage concentration be 1%) is added after reaction and terminates reaction, products therefrom
It is washed with a large amount of methanol, vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer
0.6g, number-average molecular weight 11000, molecular weight distribution 1.35, the molar content of PPO segment is in copolymer
The molar content of 10%, PLA segment is that the molar content of 54%, PPC segment is 36%, and the vitrifying of copolymer turns
Temperature is 39 DEG C, elongation at break 73%, tensile strength 33MPa.
Embodiment 4
SalenCr (the OC as shown in above formula6H2(NO2)3) catalyst 21mg (0.035mmol), co-catalyst
PPNCl40mg (0.07mmol) and propylene oxide 12.2mL (175mmol), is separately added into autoclave (molar ratio
SalenCr(OC6H2(NO2)3) catalyst: co-catalyst: propylene oxide=1:2:5000), polymeric reaction temperature is 60 DEG C, instead
After answering 18 hours, the propylene oxide 12.5mL of lactide 2.52g (molar ratio of lactide and propylene oxide is 1:50) is added
Solution then carbon dioxide is filled with into autoclave rapidly after reaction 1 hour, pressure maintains 3.5MPa in kettle, reaction
Time is 22 hours, and 100mL hydrochloric acid methanol (HCl mass percentage concentration is 1%) is added after reaction and terminates reaction, gained
Product is washed with a large amount of methanol, and vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer
3g, number-average molecular weight 17000, molecular weight distribution 1.3, the molar content of PPO segment is 13% in copolymer,
The molar content of PLA segment is that the molar content of 35%, PPC segment is 52%, the glass transition temperature of copolymer
Degree is 35 DEG C, elongation at break 153%, tensile strength 23MPa.
Embodiment 5
Porphyrin aluminium PorphyrinAl (OEt) catalyst 23.9mg (0.035mmol), co-catalyst as shown in above formula
PPNCl20mg (0.035mmol) and propylene oxide 12.2mL (175mmol), is separately added into autoclave (molar ratio porphyrin
Aluminium PorphyrinAl (OEt) catalyst: co-catalyst: propylene oxide=1:1:5000), polymeric reaction temperature is 60 DEG C, reaction
After 8 hours, the methylene chloride 10mL solution of lactide 2.52g (molar ratio of lactide and propylene oxide is 1:10) is added,
After reaction 1 hour, then it is filled with carbon dioxide to autoclave rapidly, pressure maintains 3.5MPa, reaction time 22 in kettle
Hour, 100mL methanol hydrochloride solution (HCl mass percentage concentration is 1%) is added after reaction and terminates reaction, products therefrom is used
A large amount of methanol washings, vacuum drying obtain white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer 3.2g,
Its number-average molecular weight is 18700, molecular weight distribution 1.43, and the molar content of PPO segment is 3%, PLA chain in copolymer
The molar content of section is that the molar content of 28%, PPC segment is 69%, and the glass transition temperature of copolymer is 35
DEG C, elongation at break 194%, tensile strength 21MPa.
Embodiment 6
(O (the C of the PorphyrinAl as shown in above formula6H3(NO2)2) catalyst 26.6mg (0.035mmol), co-catalysis
Agent DMAP 4.27mg (0.035mmol) and propylene oxide 12.2mL, is separately added into autoclave (molar ratio
PorphyrinAl(O(C6H3(NO2)2) catalyst: co-catalyst: propylene oxide=1:1:5000), polymeric reaction temperature 25
DEG C, after reaction 24 hours, add the propylene oxide of lactide 5.04g (molar ratio of lactide and propylene oxide is 1:5)
12.5mL solution after reaction 2 hours, then is filled with rapidly carbon dioxide into kettle, and pressure maintains 3.5MPa, reaction time in kettle
It is 48 hours, 100mL methanol hydrochloride solution (HCl mass percentage is 1%) is added after reaction and terminates reaction, gained produces
Object is washed with a large amount of methanol, and vacuum drying obtains white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer
5.5g, number-average molecular weight 25500, molecular weight distribution 1.5, the molar content of PPO segment is 15% in copolymer,
The molar content of PLA segment is that the molar content of 67%, PPC segment is 18%, the glass transition temperature of copolymer
Degree is 39 DEG C, elongation at break 97%, tensile strength 30MPa.
Embodiment 7
The PorphyrinCrCl catalyst 37.6mg (0.035mmol) as shown in above formula, co-catalyst 2,6- dimethyl
Pyridine 7.5g (0.07mmol) and propylene oxide 12.2mL, is separately added into 100mL autoclave that (PorphyrinCrCl is urged
Agent: co-catalyst: lactide: propylene oxide=1:2:500:5000 (molar ratio)), polymeric reaction temperature is 60 DEG C, reaction
After 30min, the dioxane 10mL solution of lactide 2.52g (molar ratio of lactide and propylene oxide is 1:10) is added,
After reaction 1 hour, then carbon dioxide is filled with into autoclave rapidly, pressure maintains 1MPa, reaction time 15 in kettle
Hour, 100mL methanol hydrochloride solution (HCl mass percentage concentration is 1%) is added after reaction and terminates reaction, products therefrom is used
A large amount of methanol washings, vacuum drying obtain white polyethers-polylactide-fatty poly-ester carbonate ternary block polymer 2.8g,
Its number-average molecular weight is 14600, molecular weight distribution 1.5, and the molar content of PPO segment is 23%, PLA chain in copolymer
The molar content of section is that the molar content of 11%, PPC segment is 66%, and the glass transition temperature of copolymer is 2
DEG C, elongation at break 331%, tensile strength 6MPa.
Embodiment 8
The PorphyrinCoCl catalyst 37.3mg (0.035mmol) as shown in above formula, co-catalyst PPNCl 20mg
(0.035mmol) and propylene oxide 0.98mL (14mmol) are separately added into autoclave, and molar ratio PorphyrinCoCl is urged
Agent: co-catalyst: propylene oxide=1:1:400, polymeric reaction temperature are 100 DEG C, after reaction 4 hours, add lactide
The dioxane 10mL solution of 2.016g (molar ratio of lactide and propylene oxide be 1:1), after reaction 6 hours, then rapidly to
Carbon dioxide is filled in autoclave, pressure maintains 3.5MPa in kettle, and the reaction time is 22 hours, is added after reaction
100mL hydrochloric acid methanol terminates reaction, and products therefrom is washed with a large amount of methanol, and vacuum drying obtains white polyethers-polylactide-rouge
Fat adoption carbonic ester ternary block polymer 2.1g, number-average molecular weight 10000, molecular weight distribution 1.25, in copolymer
The molar content of PPO segment is that the molar content of 10%, PLA segment is the molar content of 27%, PPC segment
It is 63%, the glass transition temperature of copolymer is 33 DEG C, elongation at break 205%, tensile strength 18MPa.
Embodiment 9
PorphyrinAl (the OOCCCl as shown in above formula3) catalyst 39mg (0.035mmol), co-catalyst PPNCl
20mg (0.035mmol) and propylene oxide 12.2mL (175mmol) are separately added into autoclave (PorphyrinAl
(OOCCCl3) catalyst: PPNCl: propylene oxide=1:1:5000 (molar ratio)), polymeric reaction temperature is 60 DEG C, and reaction 20 is small
Shi Hou adds the dioxane 10mL solution of lactide 2.52g (molar ratio of lactide and propylene oxide is 1:10), instead
After answering 1 hour, then carbon dioxide is filled with into autoclave rapidly, pressure maintains 3.5MPa, reaction time 22 in kettle
Hour, hydrochloric acid methanol is added after reaction and terminates reaction, products therefrom is washed with a large amount of methanol, obtains white polyethers-poly- third
Lactide-fatty poly-ester carbonate ternary block polymer 3.2g, number-average molecular weight 14000, molecular weight distribution 1.1, altogether
The molar content of PPO segment is moles hundred that the molar content of 14%, PLA segment is 31%, PPC segment in polymers
Dividing content is 55%, and the glass transition temperature of copolymer is 35 DEG C, elongation at break 187%, tensile strength 20MPa.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (5)
1. polyethers-polylactide-fatty poly-ester carbonate ternary block polymer method is prepared using composite catalyst, it is special
Sign is: metal salen catalyst or catalysis of metalloporphyrin agent and co-catalyst, propylene oxide being added in autoclave, instead
It answers 0.5-24 hours, lactide is added, reaction time 1-6 hour makes in kettle into autoclave full of carbon dioxide rapidly
Pressure maintains 1.0-5.0MPa, polymerization reaction, and a large amount of methanol hydrochloride solutions are added after polymerization reaction and terminate reaction, gained
Product is washed to obtain polyethers-polylactide-fatty poly-ester carbonate ternary block polymer with a large amount of methanol；
The composite catalyst is made of metal salen catalyst with co-catalyst, and metal salen catalyst and co-catalyst rub
Your ratio is 1:0.5-2, wherein the structural formula of metal salen catalyst are as follows:
M=Cr or Co；R1=-C6H4Ortho position di-substituted-phenyl, 1,2- cyclohexyl ,-CH2CH2Or-CH (CH3)CH2-；R2=
CH3,t-Bu；R3=Br, CH3, t-Bu or CH2Cl；X is-Cl, CF3COO-, 2,4-DNP oxygroup or 2,4,6- trinitro-s
Phenol oxygroup；
The co-catalyst is double-(dihalotriphenylphosphoranes base) ammonium chloride, 4-dimethylaminopyridine or 2,6- lutidines；
Alternatively,
The composite catalyst is made of catalysis of metalloporphyrin agent with co-catalyst, and catalysis of metalloporphyrin agent and co-catalyst rub
Your ratio is 1:0.5-2, wherein the structural formula of catalysis of metalloporphyrin agent are as follows:
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 oxygroup；
The co-catalyst is double-(dihalotriphenylphosphoranes base) ammonium chloride, 4-dimethylaminopyridine or 2,6- lutidines.
2. according to the method described in claim 1, it is characterized in that the lactide is dissolved in propylene oxide or appropriate solvent,
The molar ratio of lactide and propylene oxide or solvent is 1:5-10；The solvent is methylene chloride, toluene or dioxane.
3. according to the method described in claim 1, it is characterized in that metal salen catalyst or catalysis of metalloporphyrin agent are urged with helping
The molar ratio of agent is 1:0.5-2, the molar ratio of metal salen catalyst or catalysis of metalloporphyrin agent and propylene oxide is 1:
100-5000。
4. according to the method described in claim 1, it is characterized in that the molar ratio of lactide and propylene oxide is 1:1-50.
5. according to the method described in claim 1, it is characterized in that polymeric reaction temperature be 25-100 DEG C, reaction time 15-
48 hours.
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| CN107739432A (en) * | 2017-12-05 | 2018-02-27 | 桐乡守敬应用技术研究院有限公司 | A kind of barrier mulch film |
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| CN108395510B (en) * | 2018-02-06 | 2020-01-31 | 浙江大学 | Catalytic system and application thereof in preparation of carbon dioxide-based polycarbonate block copolymer |
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