CN109337055A - A kind of preparation method of the polylactic acid block polymer of Stereocomplex crystal type - Google Patents
A kind of preparation method of the polylactic acid block polymer of Stereocomplex crystal type Download PDFInfo
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- CN109337055A CN109337055A CN201811178912.2A CN201811178912A CN109337055A CN 109337055 A CN109337055 A CN 109337055A CN 201811178912 A CN201811178912 A CN 201811178912A CN 109337055 A CN109337055 A CN 109337055A
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
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Abstract
The present invention is a kind of preparation method of the polylactic acid block polymer of Stereocomplex crystal type, and the polylactic acid block polymer being made of different optical activity segments is prepared using inert gas shielding method.It under the action of catalyst, is that initiator causes levorotatory lactide synthetic prepolymer, then using prepolymer as macromole evocating agent, causes dextrorotation lactide and carry out ring-opening polymerisation, required product is prepared using functional end-group as the racemosus polyethers or polyester of hydroxyl.The present invention, by simple reaction process, can prepare the polylactic-acid block copolymer that number-average molecular weight is up to 10 ~ 300,000 under normal pressure inert atmosphere without high vacuum condition.The polylactic acid of preparation generates Stereocomplex crystallographic texture, and Stereocomplex crystallization behavior only occurs in multi source heating melting process, and the homopolymer crystallization of low melting point will not occur.The fusing point for the polylactic acid block polymer being prepared is up to 210 ~ 230 DEG C, and has many advantages, such as that molecular structure is controllable, and steric regularity is high, has broad application prospects.
Description
Technical field
The invention belongs to synthesis of polymer material technical field more particularly to a kind of polylactic acid of Stereocomplex crystal type are embedding
The preparation method of section polymer.
Background technique
With the fast development of world economy, petroleum resources are increasingly depleted, and natural environment locating for the mankind is worsening, seek
Environment amenable material is looked for become the hot spot of current research.Polylactic acid (Polylactide, PLA) is as a kind of with can be again
Plant resource is the environmentally protective plastics that raw material after chemical reaction is prepared, and has good biodegradability and life
Object compatibility, catabolite in the natural environment are carbon dioxide and water, no pollution to the environment.Therefore, PLA material is recognized
To be one of the renewable polymer material for most having researching value and application prospect, in bio-medical, bio-pharmaceuticals, food outsourcing
It is filled with and the fields such as routine office work articles has been widely used.Compared with conventional petroleum based high molecular material, although
PLA material has good mechanical property and biocompatibility, but still has some performances to be improved, and such as lower melt is strong
Degree and crystal property, heat distortion temperature only have 58 DEG C or so, and heat resistance is poor, the mechanical properties decrease etc. of product after hot-working
Disadvantage greatly limits PLA in application (Macromolecules, 20 (1987): 904- in engineering material field
906).It is necessary for being modified at present for disadvantage mentioned above to PLA.
Using the optical isomerism characteristic of PLA material, by the Poly L-lactic acid (P with different optical activitiesL) and poly- dextrorotation LA
Lactic acid (PDThe fusing point of stereocomplex PLA (Sterecomplex PLA, the sc-PLA) material LA) being blended is compared
About 50 DEG C are improved in the fusing point of homopolymer, this method greatly improves the heat resistance of PLA, so that as high-performance engineering
The application range of the PLA material of material becomes wide.In addition, sc-PLA material has preferable mechanical property and hydrolytic resistance etc. excellent
Point has very important application value.
There are mainly two types of for the current method for preparing sc-PLA: (1) will be different using solution or melt-mixing method
The P of ratioLLA and PDLA carries out that preparation sc-PLA material is blended, and this method is easy to operate；It (2) will using the method for block copolymerization
The P of different proportionLLA and PDP is prepared by ring-opening polymerisation in LALLA-PDLA block copolymer (Stereoblock, sb-
PLA), and then the higher sc-PLA of purity is obtained.
Patent CN102532837A discloses a kind of preparation method of the polylactic acid stereoscopic composite of high molecular weight, i.e., will
PLLA and PDMixture is placed in torque rheometer and mixes by different quality ratio mixing, and under the conditions of 140 ~ 210 DEG C by LA,
It is prepared for the sc-PLA of high molecular weight.However, when using the above melt or solution blended process preparation sc-PLA, due to PLLA and
PDCompatibility between LA segment is poor, particularly evident especially for the PLA of high molecular weight, along with the same of generation sc-PLA
When, easily generation PLLA and PDLA homopolymer crystal, and the molecular structure of obtained sc-PLA is uncontrollable, seriously affects product
Thermodynamic property (Macromolecules, 40 (2007): 1049-1054).
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type,
With the cumbersome step of the existing synthetic technology of simplification, industrial mass production is realized.
A kind of preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type proposed by the present invention, it is lazy using normal pressure
Property gas protection method, using nonlinear functional end-group be hydroxyl racemosus polyethers or polyester, under the effect of the catalyst
Cause levorotatory lactide ring-opening polymerisation, the Poly L-lactic acid prepolymer of racemosus is prepared.Then left-handed cream is gathered with racemosus
Sour prepolymer causes corresponding optical isomerism lactide monomer and ring-opening polymerization occurs, be prepared into as macromole evocating agent
To the polylactic-acid block copolymer of high molecular weight.Specific step is as follows:
(1) under anhydrous and inert gas shielding, three mouthfuls of burnings are added according to mass ratio for 1:15 in initiator and levorotatory lactide
In bottle, proper catalyst is added, is warming up to 145-160 DEG C of 24 ~ 36 h of reaction after mixing evenly, the poly- left side of racemosusization is prepared
Revolve lactic acid prepolymer crude product；
(2) the racemosus Poly L-lactic acid prepolymer crude product that step (1) is prepared is dissolved in organic solvent, is sunk
It forms sediment, removes unreacted monomer and low-molecular-weight oligomer, cleaned after precipitating, drying is prepared into racemosus Poly L-lactic acid pre-polymerization
Object；
(3) the racemosus Poly L-lactic acid that step (2) is prepared is dissolved in organic solvent, dextrorotation lactide is added and urged
Agent is stirring evenly and then adding into three-necked flask, and being passed through inert gas while being warming up to 60 DEG C makes system reach vacuum state,
145-160 DEG C of 24 ~ 36 h of reaction are continuously heating to, the polylactic-acid block copolymer with Stereocomplex is prepared and slightly produces
Object；
(4) the polylactic-acid block copolymer crude product with Stereocomplex that step (3) is prepared is dissolved in trichlorine
It in the mixed organic solvents of methane and hexafluoroisopropanol, is precipitated later, removes unreacted monomer and low-molecular-weight oligomer,
Drying, obtains the polylactic-acid block copolymer with Stereocomplex.
The beneficial effects of the present invention are:
(1) compared with prior art, the present invention solves that poly-lactic acid in high molecular weight block must be synthesized under high vacuum environment is total
This technical problem of polymers, has been prepared that molecular structure is controllable and number-average molecular weight is up to 10 ~ 300,000 has vertical structure multiple
Close the polylactic-acid block copolymer of structure.
(2) ring-opening polymerization temperature is 130 ~ 160 DEG C, and reaction condition is milder, avoids polylactic acid molecule chain
The sequential structure regularity of the generation of the side reactions such as thermal degradation and transesterification, the strand for the product being prepared is higher.
(3) chemical structure and molecular weight of product can be regulated and controled by the feed ratio of control initiator and monomer.
(4) polylactic acid prepared only generates Stereocomplex crystallographic texture, and in multi source heating melting process only
Stereocomplex crystallization behavior occurs, the homopolymer crystallographic of no low melting point generates.
Detailed description of the invention
Fig. 1 is three cladodification polyoxypropylenes-in case study on implementation 1 of the present inventionLPolylactic acid-DPolylactic-acid block copolymer
Nuclear magnetic resonance spectroscopy.
Fig. 2 is three cladodification polyoxypropylenes-in case study on implementation 1 of the present inventionLPolylactic acid-DPolylactic-acid block copolymer
Carbon-13 nmr spectra.
Fig. 3 is three cladodification polyoxypropylene of nascent state-l-polylactic acid-D- polylactic acid in present example case study on implementation X
The DSC spectrogram of block copolymer.
Fig. 4 is three cladodification polyoxypropylenes-in case study on implementation 1 of the present inventionLPolylactic acid-DPolylactic-acid block copolymer
DSC spectrogram.
Specific embodiment
With case study on implementation, the present invention is further described below, but the present invention is not intended to be limited thereto, the raw material in embodiment
It is conventional commercial product, in which:
Polylactic-acid block copolymer prepared by the present invention by nuclear magnetic resonance spectroscopy (1H NMR) determine its chemical composition, nuclear-magnetism is total
Vibration carbon spectrum (13C NMR) determine that its steric regularity, differential scanning calorimetry (DSC) measure its hot property.
Embodiment 1
(1) weigh 0.72 g number-average molecular weight be 3300 three cladodification polyoxypropylenes (PPO), 30 g levorotatory lactides (L-
LA) and 0.12 g stannous octoate, it is added in three-neck flask.While logical nitrogen, 145 DEG C are to slowly warm up to, reacts 36 h.Reaction
After, 500 mL methylene chloride of crude product are dissolved, make precipitating reagent precipitating with ethyl alcohol, are cleaned, vacuum drying obtains three
Change Poly L-lactic acid prepolymer.
(2) that three cladodification Poly L-lactic acid prepolymer obtained in step (1) is dissolved in 300 mL methylene chloride is organic molten
In liquid, 30 g dextrorotation lactides of addition (D- LA) and 0.06 g stannous octoate, three-necked flask is poured into after mixing evenly.Logical nitrogen
Meanwhile 60 DEG C are to slowly warm up to up to making system reach vacuum state, 145 DEG C are continuously heating to, 36 h are reacted.Reaction terminates
Afterwards, crude product is dissolved in 500 mL, chloroform/hexafluoroisopropanol in the mixed solvent that volume ratio is 95/5 is made with ethyl alcohol
Precipitating reagent precipitating, is cleaned, and vacuum drying obtains the polyoxypropylene-of three cladodificationLPolylactic acid-DPolylactic acid (PPO-PLLA-
PDLA) block copolymer, molecular structure is as shown in figure 1 shown in molecular formula.
Fig. 1 is three cladodification polyoxypropylenes-LPolylactic acid-DThe nuclear magnetic resonance spectroscopy of polylactic-acid block copolymer, respectively
The chemical shift ownership of proton is as shown in the figure.It can be in the hope of three cladodification epoxy third in block copolymer by the integral area at each peak
Alkane polyethers,LPolylactic acid andDThe mass ratio of polylactic acid is 1:22:22.
Fig. 2 is three cladodification polyoxypropylenes-LPolylactic acid-DThe DSC spectrogram of polylactic-acid block copolymer.Work as copolymer
After 230 DEG C of 3 mins of isothermal, the Stereocomplex crystal of l-polylactic acid and the formation of D- polylactic acid chain segment is totally disrupted sample, is quenched
It is cold to obtain random coil structure.Under the heating rate of 10 DEG C/min, it is 223 DEG C that DSC, which measures its fusing point, as shown in Figure 2.
Fig. 3 is three cladodification polyoxypropylenes-LPolylactic acid-DThe carbon-13 nmr spectra of polylactic-acid block copolymer.?
CDCl3With HFIP in the mixed solvent, PPO-PLLA-PDThere is a very strong characteristic peak at 170.67 ppm in LA, ownership
For mmmmm, rmmmm, mmmmr and the rmmmr sequential structure of Unit six.PPO-PDLA-PLThe change of the carbonylic carbon atom of LA sample
Also there is one very strong characteristic peak in 170.67 ppm in displacement study, while not occurring being attributed to outside at 170.2 ppm or so place
One relatively weak characteristic peak of racemization structure sequence unit shows that sample has high steric regularity.
Embodiment 2
(1) weigh 1.5 g number-average molecular weights be 3300 three cladodification polyoxypropylenes (PPO), 30g levorotatory lactide (L- LA)
With 0.1g stannous octoate, three-necked flask is added.While logical nitrogen, 145 DEG C are to slowly warm up to, reacts 36 h.After reaction,
Crude product is dissolved in 400 mL methylene chloride organic solvents, makees precipitating reagent precipitating with ethyl alcohol, is cleaned, vacuum drying obtains three
Cladodification Poly L-lactic acid prepolymer.
(2) that three cladodification Poly L-lactic acid prepolymer obtained in step (1) is dissolved in 300 mL methylene chloride is organic molten
In agent, 30 g dextrorotation lactides of addition (D- LA) and 0.05 g stannous octoate, it pours into three-necked flask after mixing evenly.Logical nitrogen
While, 60 DEG C are to slowly warm up to until system reaches vacuum state, are continuously heating to 145 DEG C, are reacted 12 h.Reaction terminates
Afterwards, crude product is dissolved in 500 mL, chloroform/hexafluoroisopropanol in the mixed solvent that volume ratio is 95/5 is made with ethyl alcohol
Precipitating reagent precipitating, is cleaned, and vacuum drying obtains the polyoxypropylene-of three cladodificationLPolylactic acid-DPolylactic acid (PPO-PLLA-
PDLA) block copolymer.By method listed by embodiment 1, measuring this polylactic-acid block copolymer has very high steric regularity,
And three cladodification polyoxypropylenes in block copolymer,LPolylactic acid,DThe mass ratio of polylactic acid is 1:10:10, fusing point 218
℃。
Embodiment 3
(1) weigh 0.6 g number-average molecular weight be 3500 three cladodification polyoxypropylenes (PPO), 10g levorotatory lactide (L- LA)
With 0.05g stannous octoate, it is added in three-necked flask.While logical nitrogen, 145 DEG C are to slowly warm up to, reacts 12 h.Reaction terminates
Afterwards, crude product is dissolved in 100 mL methylene chloride organic solvents, makees precipitating reagent precipitating with ethyl alcohol, cleaned, be dried in vacuo
To three cladodification Poly L-lactic acid prepolymers.
(2) that three cladodification Poly L-lactic acid prepolymer obtained in step (1) is dissolved in 100 mL methylene chloride is organic molten
In agent, 10 g dextrorotation lactides of addition (D- LA) and 0.02 g stannous octoate, it pours into three-necked flask after mixing evenly.Logical nitrogen
While, 60 DEG C are to slowly warm up to until system reaches vacuum state, are continuously heating to 145 DEG C, are reacted 12 h.Reaction terminates
Afterwards, crude product is dissolved in 300 mL, chloroform/hexafluoroisopropanol in the mixed solvent that volume ratio is 95/5 is made with ethyl alcohol
Precipitating reagent precipitating, is cleaned, and vacuum drying obtains the polyoxypropylene-of three cladodificationLPolylactic acid-DPolylactic acid (PPO-PLLA-
PDLA) block copolymer.By method listed by embodiment 1, measuring this polylactic-acid block copolymer has very high steric regularity,
And three cladodification polyoxypropylenes in block copolymer,LPolylactic acid,DThe mass ratio of polylactic acid is 1:8:8；206 DEG C of fusing point.
Claims (11)
1. the preparation method of the polylactic acid block polymer of Stereocomplex crystal type, it is characterised in that specific step is as follows:
It (1) with mass ratio is the ratio of 1:15 ~ 1:45 by initiator and levorotatory lactide under anhydrous and inert gas shielding
It is added in three-necked flask, catalyst is added, is warming up to 145-160 DEG C of 24 ~ 36 h of reaction after mixing evenly, is prepared more
Cladodification Poly L-lactic acid prepolymer crude product；
(2) the racemosus Poly L-lactic acid prepolymer crude product that step (1) is prepared is dissolved in organic solvent, it is laggard
Row precipitating, it is therefore an objective to remove unreacted monomer and low-molecular-weight oligomer, be cleaned after precipitating, be dried to get the poly- left side of racemosusization is arrived
Revolve lactic acid prepolymer；
(3) the racemosus Poly L-lactic acid prepolymer that step (2) is prepared is dissolved in solvent, be added dextrorotation lactide and
Catalyst is stirring evenly and then adding into three neck round bottom, and being passed through inert gas while being warming up to 60 DEG C reaches system
Vacuum state is continuously heating to 145-160 DEG C of 24 ~ 36 h of reaction, it is embedding that the polylactic acid with Stereocomplex is prepared
Section copolymer crude product；
(4) the polylactic-acid block copolymer crude product with Stereocomplex that step (3) is prepared is dissolved in trichlorine
It in the mixed organic solvents of methane and hexafluoroisopropanol, is precipitated later, removes unreacted monomer and low-molecular-weight oligomer,
Drying, obtains the polylactic-acid block copolymer with Stereocomplex.
2. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type according to claim 1, feature exist
In entire reaction process is under the protection of inert gas flow, and inert gas is nitrogen or argon gas, throughput 10
~ 20 dL/min。
3. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type according to claim 1, feature exist
In initiator as described in step (1) is polyoxypropylene or terminal hydroxy group polyglycolic acid ester, degree of functionality >=3, initiation used
The number-average molecular weight of agent is 2000 ~ 10000.
4. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type according to claim 1, feature exist
In catalyst described in step (1) and step (3) is metal carboxylate or metal alkoxide.
5. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type according to claim 4, feature exist
In the catalyst is one of stannous octoate, aluminium isopropoxide, stannous acetate or lactic acid stannous or a variety of.
6. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type according to claim 1, feature exist
In the mole that catalyst is added in step (1) is consistent with the terminal hydroxy group mole of initiator, and catalyst is added in step (3)
Mole is 0.5 ~ 1 times that catalyst is added in step (1).
7. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type according to claim 1, feature exist
In organic solvent described in step (2) is in methylene chloride, chloroform, toluene, dimethylbenzene, dichloro-benzenes or diphenyl ether
It is one or more.
8. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type according to claim 1, feature exist
In concentration of organic solution when dissolving crude product described in step (2) is 0.04 ~ 0.06 g/mL.
9. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type according to claim 1, feature exist
In the mass ratio of the levorotatory lactide and dextrorotation lactide that are added in step (1) and step (3) is 1:1.
10. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type according to claim 1, feature exist
In the volume ratio of chloroform and hexafluoroisopropanol is 85:15 ~ 95:5 in mixed organic solvents described in step (4).
11. the preparation method of the polylactic-acid block copolymer of Stereocomplex crystal type described in claim 1, which is characterized in that
The polymerization is ontology ring-opening polymerisation, and products therefrom polylactic-acid block copolymer is pure white floccule, and number is divided equally
Son amount is 1 × 105 ~ 4×105 g/mol。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812348A (en) * | 2021-02-26 | 2021-05-18 | 江南大学 | High-heat-resistance anti-ultraviolet polylactic acid/nano lignin composite membrane and preparation method thereof |
| CN115491004A (en) * | 2022-09-16 | 2022-12-20 | 江南大学 | Preparation method and application of long-chain branched polylactic acid |
-
2018
- 2018-10-10 CN CN201811178912.2A patent/CN109337055A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812348A (en) * | 2021-02-26 | 2021-05-18 | 江南大学 | High-heat-resistance anti-ultraviolet polylactic acid/nano lignin composite membrane and preparation method thereof |
| CN112812348B (en) * | 2021-02-26 | 2022-04-29 | 江南大学 | High-heat-resistance anti-ultraviolet polylactic acid/nano lignin composite membrane and preparation method thereof |
| CN115491004A (en) * | 2022-09-16 | 2022-12-20 | 江南大学 | Preparation method and application of long-chain branched polylactic acid |
| CN115491004B (en) * | 2022-09-16 | 2023-11-14 | 江南大学 | Preparation method and application of long-chain branched polylactic acid |
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Application publication date: 20190215 |