CN107216451A - A kind of method of PLA spontaneous nucleation - Google Patents

A kind of method of PLA spontaneous nucleation Download PDF

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Publication number
CN107216451A
CN107216451A CN201710448174.8A CN201710448174A CN107216451A CN 107216451 A CN107216451 A CN 107216451A CN 201710448174 A CN201710448174 A CN 201710448174A CN 107216451 A CN107216451 A CN 107216451A
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pla
hydrogen bond
intermediate product
chemical constitution
temperature
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CN107216451B (en
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余鳗漫
马丕明
沈田丰
东为富
陈明清
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Jiangnan University
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Jiangnan University
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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
    • 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
    • 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
    • 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

Abstract

The invention discloses a kind of method of PLA spontaneous nucleation, belong to technical field of polymer materials.Amide group is introduced into PLA strands is crystallized by intramolecular spontaneous nucleation induced polymer first by the present invention, the method of PLA spontaneous nucleation proposed by the present invention, abundant polymer nucleation and crystallization theory, and the plastic products of physical and mechanical properties and Good Heat-resistance can be prepared.The hydridization type PLA of hydrogen bond group is carried on the main chain of the present 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 PLA is improved to 38% by 0%, flexible chain is foreshortened within 5min by 40min.

Description

A kind of method of PLA spontaneous nucleation
Technical field
The present invention relates to a kind of method of PLA spontaneous nucleation, belong to technical field of polymer materials.
Background technology
PLA (PLA) is considered as one of current most promising bio-based and biodegradated polymer materal, is possessed Excellent physical and mechanical properties, processing characteristics and good biocompatibility, has wide in fields such as medical treatment, packaging, weavings Application prospect.But low, the molding cycle length of heat distortion temperature etc. is asked caused by PLA is because crystalline rate is slow, crystallinity is low Topic, largely limits the application and development of PLA material.
At present, outer Added Nucleating Agents are to improve PLA crystalline rates and crystallinity is most simple, maximally effective means.But at present The method that crystalline rate and crystallinity are improved by outer Added Nucleating Agents, outer Added Nucleating Agents easily in PLA matrix disperse Inequality, influences the physical and mechanical properties and processing characteristics of material；On the other hand, outer Added Nucleating Agents need extra increase premixing Step, it is cumbersome, increase cost.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the invention provides a kind of method of PLA spontaneous nucleation.The present invention Amide group is introduced into PLA strands, crystallized by intramolecular spontaneous nucleation induced polymer, present invention aims at propose one The method for planting PLA spontaneous nucleation, enriches polymer nucleation and crystallization theory.
First purpose of the present invention is to provide a kind of method of PLA spontaneous nucleation, the method for the PLA spontaneous nucleation Comprise the following steps：
(1) hydrogen bond group with self assembly nucleation is introduced in PLA building-up process, molecular backbone is obtained The upper PLA containing one or more hydrogen bond groups；
(2) PLA with hydrogen bond group on molecular backbone is warming up to 1-50 DEG C of the melting temperature above and constant temperature 0.05-5min, then cools or in the following constant temperature of fusing point；
(3) in temperature-fall period or thermostatic process, PLA can occur certainly by the hydrogen bond action between hydrogen bond group Nucleation, and induce polylactic acid chain segment rapid crystallization.
In one embodiment, the chemical constitution 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 below PLA melting temperature.
In one embodiment, the PLA containing one or more hydrogen bond groups has the change of (I) or (II) Learn structure：
Wherein, n is the integer more than 10；P is the integer between 1~9.
Second object of the present invention is to provide a kind of hydridization type PLA, and the hydridization type lactic acid has (I) or (II) Architectural feature：
Wherein, n is the integer more than 10；P is the integer between 1~9
In one embodiment, the hydridization type PLA can be prepared by the following：First by ethanedioic acid two Ethyl ester directly synthesizes terminal hydroxy group intermediate product A with monoethanolamine reaction, then triggers lactide ring-opening polymerisation to obtain using intermediate product A The chemical constitution containing hydrogen bond group is the hydridization type PLA of (I) on to a kind of molecular backbone；Intermediate product A chemical constitution Such as (III)：
In another embodiment, the hydridization type PLA can be prepared by the following：The PLA can To be prepared by the following：Diethyl oxalate and diamine are first reacted into synthetic mesophase product B, then by intermediate product B Terminal hydroxy group intermediate product C is obtained with monoethanolamine reaction, finally triggers lactide ring-opening polymerisation using intermediate product C, obtains one kind The chemical constitution containing hydrogen bond group is the hydridization type PLA of (II) on molecular backbone；Intermediate product B chemical constitution is such as (IV)：
Intermediate product C chemical constitution such as (V)：
In one embodiment, the diamine can for ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, certain herbaceous plants with big flowers diamines, One kind in hendecane diamines, dodecamethylene diamine, tetradecane diamines, octadecamethylene diamine.
In one embodiment, the reaction for triggering internal ester monomer to polymerize is in stannous octoate or stannous iso caprylate Catalysis is lower to be carried out.
In one embodiment, the hydridization type polyester is
In one kind.
The hydridization type polyester with hydrogen bond group can be as nucleator in PLA matrix on the main chain of the present invention In use, its consumption be 5~95%.
Beneficial effects of the present invention：
(1) amide group is introduced into PLA strands is crystallized by intramolecular spontaneous nucleation induced polymer first by the present invention Model, the method for PLA spontaneous nucleation proposed by the present invention enriches polymer nucleation and crystallization theory.
(2) the hydridization type polyester of hydrogen bond group is carried on main chain of the invention, can induce poly- by intramolecular spontaneous nucleation Compound is crystallized, and rapid crystallization can occur at relatively high temperatures, the crystallinity of PLA is improved to 38% by 0%, during hypocrystalline Between foreshortened to by 40min within 5min.
Brief description of the drawings
Fig. 1 is petrographic microscope (POM) photograph of comparative example 1 of the present invention and the gained PLA of embodiment 1 and hydridization PLA Piece；
Fig. 2 is the nucleus magnetic hydrogen spectrum of the gained hydridization PLA of embodiments of the invention 4；
Fig. 3 is the infrared spectrogram of the gained hydridization PLA of embodiments of the invention 4.
Embodiment
Embodiment is given below so that the present invention to be specifically described, but it is necessarily pointed out that following examples It is only used for that the present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the technology in the field is ripe Practice personnel and protection scope of the present invention is still belonged to some nonessential modifications and adaptations of the invention made according to present invention.
Embodiment 1
By diethyl oxalate and ethylenediamine in molar ratio 10:1 weighs, using constant pressure funnel by ethylenediamine/tetrahydrochysene Tetrahydrofuran solution is slowly added dropwise into the tetrahydrofuran solution of excessive diethyl oxalate, and 24h is stirred at room temperature, white suspension is obtained Liquid, intermediate product A is obtained after filtering, washing, drying.By intermediate product A and monoethanolamine in molar ratio 10:1 weighs, and uses constant pressure Intermediate product A/ chloroformic solutions are slowly added dropwise into the tetrahydrofuran solution of the amine containing excess ethyl alcohol dropping funel, heating stirring, Flow back 24h, obtains white suspension, intermediate product B is obtained after filtering, washing, drying.Weigh lactide and intermediate product B by Certain mol proportion feeds intake in toluene solution, adds 0.5wt% stannous octoates, N2Under atmosphere, heating stirring, flow back 24h, obtains White suspension, obtains a kind of PLA containing multiamide group, its structural formula is as follows after centrifugation, washing, drying.Profit The molecular weight of gained PLA is characterized with crystal property with GPC and DSC, as a result as 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 the hydridization PLA that obtained product represents for structure above really.
Embodiment 2
By diethyl oxalate and hexamethylene diamine in molar ratio 10:1 weighs, using constant pressure funnel by hexamethylene diamine/tetrahydrochysene Tetrahydrofuran solution is slowly added dropwise into the tetrahydrofuran solution of excessive diethyl oxalate, and 24h is stirred at room temperature, white suspension is obtained Liquid, intermediate product A is obtained after filtering, washing, drying.By intermediate product A and monoethanolamine in molar ratio 10:1 weighs, and uses constant pressure Intermediate product A/ chloroformic solutions are slowly added dropwise into the tetrahydrofuran solution of the amine containing excess ethyl alcohol dropping funel, heating stirring, Flow back 24h, obtains white suspension, intermediate product B is obtained after filtering, washing, drying.Weigh lactide and intermediate product B by Certain mol proportion feeds intake in toluene solution, adds 0.5wt% stannous octoates, N2Under atmosphere, heating stirring, flow back 8h, obtains White suspension, obtains a kind of PLA containing multiamide group, its structural formula is as follows after centrifugation, washing, drying.Profit The molecular weight of gained PLA is characterized with crystal property with GPC and DSC, as a result as 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 PLA that structure formula is represented.
Embodiment 3
By diethyl oxalate and hexamethylene diamine in molar ratio 10:1 weighs, using constant pressure funnel by hexamethylene diamine/tetrahydrochysene Tetrahydrofuran solution is slowly added dropwise into the tetrahydrofuran solution of excessive diethyl oxalate, and 24h is stirred at room temperature, white suspension is obtained Liquid, intermediate product A is obtained after filtering, washing, drying.By intermediate product A and monoethanolamine in molar ratio 10:1 weighs, and uses constant pressure Intermediate product A/ chloroformic solutions are slowly added dropwise into the tetrahydrofuran solution of the amine containing excess ethyl alcohol dropping funel, heating stirring, Flow back 24h, obtains white suspension, intermediate product B is obtained after filtering, washing, drying.Weigh lactide and intermediate product B by Certain mol proportion feeds intake in toluene solution, adds 0.5wt% stannous octoates, N2Under atmosphere, heating stirring, flow back 12h, obtains White suspension, obtains a kind of PLA containing multiamide group, its structural formula is as follows after centrifugation, washing, drying.Profit The molecular weight of gained PLA is characterized with crystal property with GPC and DSC, as a result as 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 said structure really The hydridization PLA that formula is represented.
Embodiment 4
By diethyl oxalate and monoethanolamine in molar ratio 1:2 measure, using constant pressure funnel by diethyl oxalate Ethanol solution instill monoethanolamine ethanol solution in, 24h is stirred at room temperature, white suspension is obtained.After filtering, washing, drying Obtain intermediate product.By lactide, intermediate product and stannous iso caprylate in mass ratio 20:1:1 weighs, N2Under atmosphere, 135 DEG C melt Melt reaction 4h, obtain a kind of PLA containing multiamide group after filtering, washing, drying, its structural formula is as follows.Utilize GPC and DSC is characterized to the molecular weight of gained PLA with crystal property, as a result as 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 the hydridization that obtained product represents for structure above really PLA.
Embodiment 5
By diethyl oxalate and monoethanolamine in molar ratio 1:2 measure, using constant pressure funnel by diethyl oxalate Ethanol solution instill monoethanolamine ethanol solution in, 24h is stirred at room temperature, white suspension is obtained.After filtering, washing, drying Obtain intermediate product.By lactide, intermediate product and stannous iso caprylate in mass ratio 20:1:1 weighs, N2Under atmosphere, 135 DEG C melt Melt reaction 24h, obtain a kind of PLA containing multiamide group after filtering, washing, drying, its structural formula is as follows.Profit The molecular weight of gained PLA is characterized with crystal property with GPC and DSC, as a result as 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 the hydridization that obtained product represents for structure above really PLA.
Comparative example 1
By lactide and stannous iso caprylate in mass ratio 20:1 weighs, N2Under atmosphere, 135 DEG C of frit reaction 4h are filtered, washed Wash, dry after obtain pure PLA, its structural formula is as follows.The molecular weight to gained PLA and crystallization using GPC and DSC Performance is characterized, as a result as shown in table 1.
It should be noted that lactide used is dried in vacuo before at 35 DEG C in various embodiments above and comparative example 12 hours.Diethyl oxalate used, monoethanolamine, ethylenediamine, hexamethylene diamine, tetrahydrofuran, stannous iso caprylate are traditional Chinese medicines collection Chemical reagent Co., Ltd of group product, purity is pure to analyze.
Above-mentioned high performance liquid chromatograph (GPC) is characterized as using PS standard curves, uses Waters THF type efficient liquid phases Chromatograph is characterized to the molecular weight of gained PLA, and gained test result is listed in Table 1 below.
The specific method of testing that above-mentioned differential scanning calorimeter (DSC) characterizes step is as follows：
Nonisothermal crystallization：30 DEG C, insulation are warming up to more than gained PLA fusing point from 0 DEG C with 10 DEG C/min heating rate 3min then drops to 0 DEG C, the fusing point (T of test gained PLA to eliminate thermal history with 10 DEG C/min rate of temperature fallm), knot Brilliant temperature (Tc) and crystallization enthalpy, gained test result is listed in Table 1 below.
Isothermal crystal：30 DEG C, insulation are warming up to more than gained PLA fusing point from 0 DEG C with 10 DEG C/min heating rate 3min is then down to 30 DEG C, constant temperature below gained PLA fusing point to eliminate thermal history with 50 DEG C/min rate of temperature fall 120min, tests gained PLA flexible chain (t at such a temperature1/2), gained test result is listed in Table 1 below.
The PLA performance of the not be the same as Example of table 1
It can be seen from the results above that the PLA obtained in comparative example 1 is difficult to crystallize in DSC test temperature-fall periods. Compared with the gained PLA of comparative example 1, the PLA of the phosphinylidyne-containing amine group obtained in embodiment 1~5 can be at relatively high temperatures Generation rapid crystallization, the crystallinity of PLA is improved to 38% by 0%, flexible chain is foreshortened within 5min by 40min. The inducible PLA of introducing that result above analyzes visible multiamide group realizes that intramolecular spontaneous nucleation promotes crystallization process, significantly Improve the crystallization temperature and crystallinity of PLA.The PLA 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 is piled into original nucleus there is provided reduced while a large amount of nucleation sites Activation energy needed for strand crystallization, induction PLA strands promote polylactic acid crystal process in its surface quickly and orderly arrangement.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and changed.Therefore, the invention is not limited in the embodiment of foregoing description, all spirit in the present invention Within principle, any modification, equivalent substitution and improvements done etc. should be included in the scope of the protection.

Claims (10)

1. a kind of method of PLA spontaneous nucleation, it is characterised in that the method for the PLA spontaneous nucleation comprises the following steps：
(1) hydrogen bond group with self assembly nucleation is introduced in PLA building-up process, obtains and contains on molecular backbone There is the PLA of one or more hydrogen bond groups；
(2) PLA with hydrogen bond group on molecular backbone is warming up to 1-50 DEG C of the melting temperature above and constant temperature 0.05- 5min, then cools 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 PLA, and Induce polylactic acid chain segment rapid crystallization.
2. according to the method described in claim 1, it is characterised in that the chemical constitution of the hydrogen bond group is-NH-CO-CO- NH-。
3. according to the method described in claim 1, it is characterised in that the rate of temperature fall of the temperature-fall period is 1-100 DEG C/min.
4. according to the method described in claim 1, it is characterised in that the temperature of the constant temperature is 5- below PLA melting temperature 80℃。
5. according to the method described in claim 1, it is characterised in that the PLA tool containing one or more hydrogen bond groups There are (I) or (II) chemical constitution：
Wherein, n is the integer more than 10；P is the integer between 1~9.
6. method according to claim 5, it is characterised in that contain one or more hydrogen bond groups on the molecular backbone PLA be prepared by the following：Diethyl oxalate is directly synthesized into terminal hydroxy group intermediate product with monoethanolamine reaction first A, then triggers lactide ring-opening polymerisation to obtain the chemical constitution containing hydrogen bond group on a kind of molecular backbone using intermediate product A For the hydridization type PLA of (I)；Intermediate product A chemical constitution is (III)：
7. method according to claim 5, it is characterised in that contain one or more hydrogen bond groups on the molecular backbone PLA be prepared by the following：Diethyl oxalate and diamine are first reacted into synthetic mesophase product B, then by centre Product B obtains terminal hydroxy group intermediate product C with monoethanolamine reaction, finally triggers lactide ring-opening polymerisation using intermediate product C, obtains The chemical constitution containing hydrogen bond group is the hydridization type PLA of (II) on a kind of molecular backbone；Intermediate product B chemical constitution For (IV)：
Intermediate product C chemical constitution is (V)：
8. according to the method described in claim 1, it is characterised in that the diamine be ethylenediamine, propane diamine, butanediamine, oneself One kind in diamines, certain herbaceous plants with big flowers diamines, hendecane diamines, dodecamethylene diamine, tetradecane diamines, octadecamethylene diamine.
9. a kind of hydridization type PLA, the hydridization type lactic acid has the architectural feature of (I) or (II)：
Wherein, n is the integer more than 10；P is the integer between 1~9.
10. a kind of application of the hydridization type polyester described in claim 9, it is characterised in that the hydridization type polyester have from into Core is acted on, and can be used as nucleator in PLA matrix, and its consumption is 5~95%.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107915967A (en) * 2017-12-14 2018-04-17 中国石油大学(北京) A kind of method of high molecular material spontaneous nucleation
CN112094401A (en) * 2020-09-27 2020-12-18 江南大学 Degradable polyester and preparation method and application thereof
CN112126203A (en) * 2020-09-27 2020-12-25 江南大学 Rapid crystallization polyester material and preparation method and application thereof
CN112608460A (en) * 2020-09-27 2021-04-06 江南大学 Polyglycolic acid material and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101631821A (en) * 2007-03-16 2010-01-20 东丽纤维研究所（中国）有限公司 Aliphatic polyester sheet and by its formed body that forms

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101631821A (en) * 2007-03-16 2010-01-20 东丽纤维研究所（中国）有限公司 Aliphatic polyester sheet and by its formed body that forms

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107915967A (en) * 2017-12-14 2018-04-17 中国石油大学(北京) A kind of method of high molecular material spontaneous nucleation
CN112094401A (en) * 2020-09-27 2020-12-18 江南大学 Degradable polyester and preparation method and application thereof
CN112126203A (en) * 2020-09-27 2020-12-25 江南大学 Rapid crystallization polyester material and preparation method and application thereof
CN112608460A (en) * 2020-09-27 2021-04-06 江南大学 Polyglycolic acid material and preparation method and application thereof
CN112094401B (en) * 2020-09-27 2021-10-19 江南大学 Degradable polyester and preparation method and application thereof
CN112608460B (en) * 2020-09-27 2022-01-11 江南大学 Polyglycolic acid material and preparation method and application thereof
CN112126203B (en) * 2020-09-27 2022-02-15 江南大学 Rapid crystallization polyester material and preparation method and application thereof

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