CN107216451B - A kind of method of polylactic acid spontaneous nucleation - Google Patents
A kind of method of polylactic acid spontaneous nucleation Download PDFInfo
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- CN107216451B CN107216451B CN201710448174.8A CN201710448174A CN107216451B CN 107216451 B CN107216451 B CN 107216451B CN 201710448174 A CN201710448174 A CN 201710448174A CN 107216451 B CN107216451 B CN 107216451B
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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Abstract
The invention discloses a kind of methods of polylactic acid spontaneous nucleation, belong to technical field of polymer materials.Amide group is introduced into PLA strand is crystallized by intramolecular spontaneous nucleation induced polymer for the first time by the present invention, the method of polylactic acid spontaneous nucleation proposed by the present invention, abundant polymer nucleation and crystallization theory, and the plastic products of physical mechanical property and Good Heat-resistance can be prepared.The hydridization type polylactic acid of hydrogen bond group is had on main chain of the invention, it can be crystallized by intramolecular amide group spontaneous nucleation induced polymer, and rapid crystallization can occur at relatively high temperatures, the crystallinity of polylactic acid is improved by 0% to 38%, flexible chain is foreshortened within 5min by 40min.
Description
Technical field
The present invention relates to a kind of methods of polylactic acid spontaneous nucleation, belong to technical field of polymer materials.
Background technique
Polylactic acid (PLA) is considered as current one of most promising biology base and biodegradated polymer materal, is possessed
Excellent physical mechanical property, processing performance and good biocompatibility has wide in fields such as medical treatment, packaging, weavings
Application prospect.But polylactic acid is asked since heat distortion temperature is low, molding cycle is long caused by crystalline rate is slow, crystallinity is low etc.
Topic largely limits the application and development of PLA material.
Currently, outer Added Nucleating Agents are to improve PLA crystalline rate and crystallinity is most simple, most effective means.But at present
The method that crystalline rate and crystallinity are improved by outer Added Nucleating Agents, outer Added Nucleating Agents are easy to disperse in polylactic acid matrix
Unevenness influences the physical mechanical property and processing performance of material；On the other hand, outer Added Nucleating Agents need additional increase premixing
Step, it is cumbersome, increase cost.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provides a kind of methods of polylactic acid spontaneous nucleation.The present invention
Amide group is introduced into PLA strand, is crystallized by intramolecular spontaneous nucleation induced polymer, present invention aims at propose one
The method of kind polylactic acid spontaneous nucleation enriches polymer nucleation and crystallization theory.
The first purpose of the invention is to provide a kind of method of polylactic acid spontaneous nucleation, the method for the polylactic acid spontaneous nucleation
The following steps are included:
(1) hydrogen bond group with self assembly nucleation is introduced in polylactic acid synthesis process, obtains molecular backbone
The upper polylactic acid containing one or more hydrogen bond groups；
(2) polylactic acid that hydrogen bond group is had on molecular backbone is warming up to above 1-50 DEG C of melting temperature and constant temperature
Then 0.05-5min cools down or in the following constant temperature of fusing point；
(3) in temperature-fall period or thermostatic process, polylactic acid can be occurred certainly by the hydrogen bond action between hydrogen bond group
Nucleation, and induce polylactic acid chain segment rapid crystallization.
In one embodiment, the chemical structure of the hydrogen bond group is-NH-CO-CO-NH-.
In one embodiment, the rate of temperature fall of the temperature-fall period is 1-100 DEG C/min.
In one embodiment, the temperature of the constant temperature is 5-80 DEG C of polylactic acid melting temperature or less.
In one embodiment, the polylactic acid containing one or more hydrogen bond groups has the change of (I) or (II)
Learn structure:
Wherein, n is the integer greater than 10；P is the integer between 1~9.
A second object of the present invention is to provide a kind of hydridization type polylactic acid, the hydridization type lactic acid has (I) or (II)
Structure feature:
Wherein, n is the integer greater than 10；P is the integer between 1~9
In one embodiment, the hydridization type polylactic acid can be prepared by the following: first by ethanedioic acid two
Ethyl ester directly reacts synthesis terminal hydroxy group intermediate product A with ethanol amine, then causes lactide ring-opening polymerisation using intermediate product A and obtains
The chemical structure containing hydrogen bond group is the hydridization type polylactic acid of (I) on to a kind of molecular backbone；The chemical structure of intermediate product A
Such as (III):
In another embodiment, the hydridization type polylactic acid can be prepared by the following: the polylactic acid can
To be prepared by the following: diethyl oxalate first being reacted to synthesis intermediate product B with diamine, then by intermediate product B
It reacts to obtain terminal hydroxy group intermediate product C with ethanol amine, finally causes lactide ring-opening polymerisation using intermediate product C, obtain one kind
Chemical structure on molecular backbone containing hydrogen bond group is the hydridization type polylactic acid of (II)；The chemical structure of intermediate product B is such as
(IV):
The chemical structure of intermediate product C such as (V):
In one embodiment, the diamine can for ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, certain herbaceous plants with big flowers diamines,
One of hendecane diamines, dodecamethylene diamine, tetradecane diamines, octadecamethylene diamine.
In one embodiment, the reaction for causing internal ester monomer polymerization is in stannous octoate or stannous iso caprylate
Catalysis is lower to be carried out.
In one embodiment, the hydridization type polyester is
One of.
Hydridization type polyester on the main chain of the invention with hydrogen bond group can be used as nucleating agent in polylactic acid matrix
Middle use, dosage are 5~95%.
Beneficial effects of the present invention:
(1) amide group is introduced into PLA strand is crystallized by intramolecular spontaneous nucleation induced polymer for the first time by the present invention
Model, the method for polylactic acid spontaneous nucleation proposed by the present invention, enrich polymer nucleation and crystallization theory.
(2) the hydridization type polyester of hydrogen bond group is had on main chain of the invention, can be induced by intramolecular spontaneous nucleation poly-
Object crystallization is closed, rapid crystallization can occur at relatively high temperatures, the crystallinity of polylactic acid is improved by 0% to 38%, when hypocrystalline
Between foreshortened within 5min by 40min.
Detailed description of the invention
Fig. 1 is petrographic microscope (POM) photograph of comparative example 1 of the present invention and 1 gained polylactic acid of embodiment and hydridization polylactic acid
Piece；
Fig. 2 is the nucleus magnetic hydrogen spectrum of 4 gained hydridization polylactic acid of the embodiment of the present invention；
Fig. 3 is the infrared spectrogram of 4 gained hydridization polylactic acid of the embodiment of the present invention.
Specific embodiment
Embodiment is given below so that the present invention to be specifically described, but it is necessarily pointed out that following embodiment
It is only used for that invention is further explained, should not be understood as limiting the scope of the invention, the technology in the field is ripe
Practice personnel's some nonessential modifications and adaptations that content makes the present invention according to the present invention and still belongs to protection scope of the present invention.
Embodiment 1
By diethyl oxalate and ethylenediamine, 10:1 is weighed in molar ratio, using constant pressure funnel by ethylenediamine/tetrahydro
Tetrahydrofuran solution is slowly added dropwise into the tetrahydrofuran solution of excessive diethyl oxalate, is stirred at room temperature for 24 hours, obtains white suspension
Liquid, be filtered, washed, dry after obtain intermediate product A.By intermediate product A and ethanol amine, 10:1 is weighed in molar ratio, uses constant pressure
Intermediate product A/ chloroformic solution is slowly added dropwise into the tetrahydrofuran solution of the amine containing excess ethyl alcohol dropping funel, heating stirring,
Reflux for 24 hours, obtain white suspension, be filtered, washed, dry after obtain intermediate product B.Weigh lactide and intermediate product B by
Certain mol proportion feeds intake in toluene solution, adds 0.5wt% stannous octoate, N2Under atmosphere, heating stirring, reflux for 24 hours, is obtained
White suspension obtains a kind of polylactic acid containing multiamide group after centrifugation, washing, drying, and structural formula is as follows.Benefit
It is characterized with molecular weight of the GPC and DSC to gained polylactic acid with crystal property, the results are shown in Table 1.
1H NMR(400MHz,DMSO)δ5.21(q,300H),3.97(s,1H),3.66(d,2H),3.40-3.30(m,
4H), 1.47 (d, 900H), it was demonstrated that obtained product is the hydridization polylactic acid that structure above indicates really.
Embodiment 2
By diethyl oxalate and hexamethylene diamine, 10:1 is weighed in molar ratio, using constant pressure funnel by hexamethylene diamine/tetrahydro
Tetrahydrofuran solution is slowly added dropwise into the tetrahydrofuran solution of excessive diethyl oxalate, is stirred at room temperature for 24 hours, obtains white suspension
Liquid, be filtered, washed, dry after obtain intermediate product A.By intermediate product A and ethanol amine, 10:1 is weighed in molar ratio, uses constant pressure
Intermediate product A/ chloroformic solution is slowly added dropwise into the tetrahydrofuran solution of the amine containing excess ethyl alcohol dropping funel, heating stirring,
Reflux for 24 hours, obtain white suspension, be filtered, washed, dry after obtain intermediate product B.Weigh lactide and intermediate product B by
Certain mol proportion feeds intake in toluene solution, adds 0.5wt% stannous octoate, N2Under atmosphere, heating stirring, flow back 8h, obtains
White suspension obtains a kind of polylactic acid containing multiamide group after centrifugation, washing, drying, and structural formula is as follows.Benefit
It is characterized with molecular weight of the GPC and DSC to gained polylactic acid with crystal property, the results are shown in Table 1.
1H NMR(400MHz,DMSO)δ5.21(q,420H),3.97(s,1H),3.66(d,2H),3.40-3.30(m,
2H), 1.86-1.75 (m, 2H), 1.61-1.51 (m, 2H), 1.47 (d, 1260H), it was demonstrated that obtained product is above-mentioned knot really
The hydridization polylactic acid that structure formula indicates.
Embodiment 3
By diethyl oxalate and hexamethylene diamine, 10:1 is weighed in molar ratio, using constant pressure funnel by hexamethylene diamine/tetrahydro
Tetrahydrofuran solution is slowly added dropwise into the tetrahydrofuran solution of excessive diethyl oxalate, is stirred at room temperature for 24 hours, obtains white suspension
Liquid, be filtered, washed, dry after obtain intermediate product A.By intermediate product A and ethanol amine, 10:1 is weighed in molar ratio, uses constant pressure
Intermediate product A/ chloroformic solution is slowly added dropwise into the tetrahydrofuran solution of the amine containing excess ethyl alcohol dropping funel, heating stirring,
Reflux for 24 hours, obtain white suspension, be filtered, washed, dry after obtain intermediate product B.Weigh lactide and intermediate product B by
Certain mol proportion feeds intake in toluene solution, adds 0.5wt% stannous octoate, N2Under atmosphere, heating stirring, flow back 12h, obtains
White suspension obtains a kind of polylactic acid containing multiamide group after centrifugation, washing, drying, and structural formula is as follows.Benefit
It is characterized with molecular weight of the GPC and DSC to gained polylactic acid with crystal property, the results are shown in Table 1.
1H NMR(400MHz,DMSO)δ5.22(q,80H),3.98(s,1H),3.65(d,2H),3.41-3.32(m,
2H), 1.85-1.73 (m, 2H), 1.62-1.51 (m, 2H), 1.47 (d, 240H), it was demonstrated that obtained product is above structure really
The hydridization polylactic acid that formula indicates.
Embodiment 4
By diethyl oxalate and ethanol amine, 1:2 is measured in molar ratio, using constant pressure funnel by diethyl oxalate
Ethanol solution instill ethanol amine ethanol solution in, be stirred at room temperature for 24 hours, obtain white suspension.After being filtered, washed, drying
Obtain intermediate product.Lactide, intermediate product and stannous iso caprylate 20:1:1 in mass ratio are weighed, N2Under atmosphere, 135 DEG C molten
Melt reaction 4h, be filtered, washed, dry after obtain a kind of polylactic acid containing multiamide group, structural formula is as follows.It utilizes
GPC and DSC characterizes the molecular weight of gained polylactic acid with crystal property, and the results are shown in Table 1.
1H NMR(400MHz,DMSO)δ8.87(s,1H),5.47(s,1H),5.28-5.14(m,35H),4.23-4.07
(m, 2H), 3.38 (s, 2H), 1.53-1.32 (m, 105H), it was demonstrated that obtained product is the hydridization that structure above indicates really
Polylactic acid.
Embodiment 5
By diethyl oxalate and ethanol amine, 1:2 is measured in molar ratio, using constant pressure funnel by diethyl oxalate
Ethanol solution instill ethanol amine ethanol solution in, be stirred at room temperature for 24 hours, obtain white suspension.After being filtered, washed, drying
Obtain intermediate product.Lactide, intermediate product and stannous iso caprylate 20:1:1 in mass ratio are weighed, N2Under atmosphere, 135 DEG C molten
Melt reaction for 24 hours, be filtered, washed, dry after obtain a kind of polylactic acid containing multiamide group, structural formula is as follows.Benefit
It is characterized with molecular weight of the GPC and DSC to gained polylactic acid with crystal property, the results are shown in Table 1.
1H NMR (400MHz, DMSO) δ 8.88 (s, 1H), 5.46 (s, 1H), 5.25-5.13 (m, 211H), 4.22-4.07
(m, 2H), 3.38 (s, 2H), 1.54-1.32 (m, 633H), it was demonstrated that obtained product is the hydridization that structure above indicates really
Polylactic acid.
Comparative example 1
Lactide and stannous iso caprylate 20:1 in mass ratio are weighed, N2Under atmosphere, 135 DEG C of frit reaction 4h are filtered, are washed
Wash, dry after obtain pure polylactic acid, structural formula is as follows.Molecular weight and crystallization using GPC and DSC to gained polylactic acid
Performance is characterized, and the results are shown in Table 1.
It should be noted that lactide used is dried in vacuo at 35 DEG C using preceding in the above various embodiments and comparative example
12 hours.Diethyl oxalate used, ethanol amine, ethylenediamine, hexamethylene diamine, tetrahydrofuran, stannous iso caprylate are traditional Chinese medicines collection
Group's chemical reagent Co., Ltd product, purity are that analysis is pure.
Above-mentioned high performance liquid chromatograph (GPC) is characterized as using Waters THF type efficient liquid phase using PS standard curve
Chromatograph characterizes the molecular weight of gained polylactic acid, and gained test result is listed in Table 1 below.
The specific test method is as follows for above-mentioned differential scanning calorimeter (DSC) characterization step:
Nonisothermal crystallization: 30 DEG C of gained polylactic acid fusing point or more, heat preservation are warming up to from 0 DEG C with the heating rate of 10 DEG C/min
3min then drops to 0 DEG C to eliminate thermal history with the rate of temperature fall of 10 DEG C/min, the fusing point (T of test gained polylactic acidm), knot
Brilliant temperature (Tc) and crystallization enthalpy, gained test result be listed in Table 1 below.
Isothermal crystal: 30 DEG C of gained polylactic acid fusing point or more, heat preservation are warming up to from 0 DEG C with the heating rate of 10 DEG C/min
3min is then down to 30 DEG C of gained polylactic acid fusing point or less, constant temperature to eliminate thermal history with the rate of temperature fall of 50 DEG C/min
120min tests gained polylactic acid flexible chain (t at such a temperature1/2), gained test result is listed in Table 1 below.
The polylactic acid performance of the different embodiments of table 1
It can be seen from the results above that polylactic acid obtained in comparative example 1 is difficult to crystallize in DSC test temperature-fall period.
Compared with 1 gained polylactic acid of comparative example, the polylactic acid of phosphinylidyne-containing amine group obtained in Examples 1 to 5 can be at relatively high temperatures
Rapid crystallization occurs, the crystallinity of polylactic acid is improved by 0% to 38%, flexible chain is foreshortened within 5min by 40min.
The introducing that result above analyzes visible multiamide group can induce polylactic acid and realize that intramolecular spontaneous nucleation promotes crystallization process, significantly
Improve the crystallization temperature and crystallinity of polylactic acid.The polylactic acid of phosphinylidyne-containing amine group is in the melt first by between amide group
Hydrogen bond action, the molecule chain haulage that will be close to amide group are piled into original nucleus, reduction while providing a large amount of nucleation sites
Activation energy needed for strand crystallization, induction PLA strand are arranged in its surface quickly and orderly, promote polylactic acid crystal process.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments of foregoing description, all in spirit of the invention
Within principle, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method of polylactic acid spontaneous nucleation, which is characterized in that the method for the polylactic acid spontaneous nucleation the following steps are included:
(1) hydrogen bond group with self assembly nucleation is introduced in polylactic acid synthesis process, is obtained and is contained on molecular backbone
There is the polylactic acid of one or more hydrogen bond groups；
(2) polylactic acid that hydrogen bond group is had on molecular backbone is warming up to above 1-50 DEG C of melting temperature and constant temperature 0.05-
Then 5min cools down or in the following constant temperature of fusing point；
(3) in temperature-fall period or thermostatic process, by the hydrogen bond action between hydrogen bond group spontaneous nucleation occurs for polylactic acid, and
Induce polylactic acid chain segment rapid crystallization；
The polylactic acid of one or more hydrogen bond groups described in step (1) has the chemical structure of (I) or (II):
Wherein, n is the integer greater than 10；P is the integer between 1~9.
2. the method according to claim 1, wherein the chemical structure of the hydrogen bond group is-NH-CO-CO-
NH-。
3. the method according to claim 1, wherein the rate of temperature fall of the temperature-fall period is 1-100 DEG C/min.
4. the method according to claim 1, wherein the temperature of the constant temperature is polylactic acid melting temperature or less 5-
80℃。
5. the method according to claim 1, wherein containing one or more hydrogen bond groups on the molecular backbone
Polylactic acid be prepared by the following: first by diethyl oxalate directly reacted with ethanol amine synthesis terminal hydroxy group intermediate product
Then A causes lactide ring-opening polymerisation using intermediate product A and obtains the chemical structure containing hydrogen bond group on a kind of molecular backbone
For the hydridization type polylactic acid of (I)；The chemical structure of intermediate product A is (III):
6. the method according to claim 1, wherein containing one or more hydrogen bond groups on the molecular backbone
Polylactic acid be prepared by the following: diethyl oxalate is first reacted with diamine to synthesis intermediate product B, then will be intermediate
Product B reacts to obtain terminal hydroxy group intermediate product C with ethanol amine, finally causes lactide ring-opening polymerisation using intermediate product C, obtains
The chemical structure containing hydrogen bond group is the hydridization type polylactic acid of (II) on a kind of molecular backbone；The chemical structure of intermediate product B
For (IV):
The chemical structure of intermediate product C is (V):
7. the method according to claim 1, wherein the diamine be ethylenediamine, propane diamine, butanediamine, oneself
One of diamines, decamethylene diamine, hendecane diamines, dodecamethylene diamine, tetradecane diamines, octadecamethylene diamine.
8. a kind of hydridization type polylactic acid, the hydridization type lactic acid has the structure feature of (I) or (II):
Wherein, n is the integer greater than 10；P is the integer between 1~9.
9. a kind of hydridization type polyester according to any one of claims 8 exists in medical treatment or weaving or the application of packaging field, feature
There is spontaneous nucleation effect in, the hydridization type polyester, can be used in polylactic acid matrix as nucleating agent, dosage for 5~
95%.
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