CN107189049A - A kind of hydridization type polyester and preparation method thereof - Google Patents
A kind of hydridization type polyester and preparation method thereof Download PDFInfo
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- CN107189049A CN107189049A CN201710447387.9A CN201710447387A CN107189049A CN 107189049 A CN107189049 A CN 107189049A CN 201710447387 A CN201710447387 A CN 201710447387A CN 107189049 A CN107189049 A CN 107189049A
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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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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a kind of hydridization type polyester and preparation method thereof, belong to technical field of polymer materials.Amide group is introduced into a kind of new hydridization type polyester material prepared in polyester molecule chain by the present invention first, further improve crystal property, heat resistance and the mechanical property of polyester, by intramolecular amide group induced polymer rapid crystallization can occur for the high performance polyester material obtained at relatively high temperatures, flexible chain shortens more than 87%, is had a wide range of applications in plastic material technical field (such as packaging, weaving, medical equipment, Phthalates or agriculture field).
Description
Technical field
The present invention relates to a kind of hydridization type polyester and preparation method thereof, belong to technical field of polymer materials.
Background technology
Polyester material is each in current national economy due to outstanding advantages such as wide, the easy to process, light weights of raw material sources
There is quite varied application in field.But (such as strength of materials is low, poor heat resistance, crystallinity for polyester material some latent defects
Can be poor) limit polyester material widely development and apply, especially as the application of engineering material.Fudan University's high score scarabaeidae
Be tied to form work(and prepared the polyester-amide copolymer based on lactic acid and alanine, and gained copolymer shows good degradability
Energy.Chinese patent CN1775827A discloses the method that melt_solid polycondensation prepares Pfansteihl and amino acid copolymer.
At present, addition filler is to improve polyester material intensity, heat resistance, crystal property most simple effective method, but is added
Plus filler easily cause and disperse inequality in the base, easily there is stress concentration, influence the physical and mechanical properties of material；The opposing party
Face, the addition of mass filler can be impacted to the processing characteristics of material.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the invention provides a kind of hydridization type polyester and preparation method thereof.
First purpose of the present invention is to provide a kind of hydridization type polyester, and the hydridization type polyester has (I) or (II)
Architectural feature：
Wherein, R1And R2For the polyester segment of carbon number 40~2300；P is the integer between 1~9.
In one embodiment, the R1And R2It is identical or different.
In one embodiment, the internal ester monomer of the polyester segment be lactide, butyrolactone, valerolactone, caprolactone,
At least one of caprylolactone.
Second object of the present invention is to provide a kind of preparation method of the hydridization type polyester.
In one embodiment, methods described includes following preparation process：
(1) by diethyl oxalate and monoethanolamine reaction synthesis terminal hydroxy group intermediate product A, chemical constitution such as (III)：
(2) trigger internal ester monomer polymerization using intermediate product A, obtain a kind of hydridization type polyester, chemical constitution such as (I)：
Wherein, R1、R2For the polyester segment of carbon number 40~2300；
P is the integer between 1~9.
In one embodiment, methods described includes following preparation process：
(1) diethyl oxalate and diamine compound are reacted into synthetic mesophase product B, chemical constitution such as (IV)：
(2) by intermediate product B and monoethanolamine reaction synthesis terminal hydroxy group intermediate product C, chemical constitution such as (V)：
(3) trigger internal ester monomer polymerization using intermediate product C, obtain a kind of hydridization type polyester, chemical constitution such as (II)：
Wherein, R1、R2For the polyester segment of carbon number 40~2300；P is the integer between 1~9.
In one embodiment, the internal ester monomer is in lactide, butyrolactone, valerolactone, caprolactone, caprylolactone
It is at least one.
In one embodiment, the diamine compound can be ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, certain herbaceous plants with big flowers
One kind in diamines, 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.
Third object of the present invention is to provide the application of the hydridization type polyester.
In one embodiment, the application be used to packing, weave, the field such as medical science, agricultural, specifically with
In packing, textile fabric, medical treatment consumptive materials, agricultural mulching etc..
Beneficial effects of the present invention：
(1) amide group is introduced into a kind of new polymer hybridisation prepared in PLA strands by the present invention first
Type polyester material, further improves crystal property, heat resistance and the mechanical property of polyester, and the high performance polyester material of acquisition exists
Engineering material technical field has a wide range of applications.
(2) there is the ester bond for being easy to degraded on hydridization type polyester of the invention, its main chain, with good degradability
Can, and the presence of amido link is conducive to the raising of its mechanical property and heat endurance.
(3) hydridization type polyester of the invention, can be crystallized by intramolecular spontaneous nucleation induced polymer, can be in higher temperature
Lower generation rapid crystallization, the crystallinity of PLA is improved to 38% by 0%, flexible chain by 40min foreshorten to 5min with
It is interior.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of the gained hydridization PLA of embodiments of the invention 1；
Fig. 2 is the infrared spectrogram of the gained hydridization PLA of embodiments of the invention 1.
Embodiment
In order to further illustrate technical scheme, the preferred embodiment of the invention is carried out with reference to embodiment
Description, but it is to be understood that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to present invention power
The limitation that profit is required.
Embodiment 1
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, a kind of hydridization PLA is obtained after filtering, washing, drying, it is as follows.Utilize NMR, FTIR, GPC and DSC couple
The structure of gained hydridization PLA is characterized with hot property, as a result as follows：Mn=5200g/mol；Tg=35 DEG C；Tm=120
℃。
As shown in figure 1, be the nucleus magnetic hydrogen spectrum of the present embodiment gained hydridization PLA,1H NMR (400MHz, DMSO) δ 8.87
(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 PLA that obtained product represents for structure above really.
As shown in Fig. 2 being the infrared spectrogram of the present embodiment gained hydridization PLA.
Embodiment 2
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 hydridization PLA after filtering, washing, drying, its structural formula is as follows.Using NMR, FTIR,
GPC and DSC is characterized to the structure of gained hydridization PLA with hot property, as a result as follows：Mn=31000g/mol；Tg=51
℃；Tm=158 DEG C.
Nucleus magnetic hydrogen spectrum information is as follows：1HNMR(400MHz,DMSO)δ8.88(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 really to be upper
State the hydridization PLA that structural formula is represented.
Embodiment 3
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, a kind of hydridization PLA is obtained after centrifugation, washing, drying, as follows.Utilize NMR, FTIR, GPC and DSC
Structure to gained hydridization PLA is characterized with hot property, as a result as follows：Mn=45000g/mol；Tg=53 DEG C；Tm=
161℃。
Nucleus magnetic hydrogen spectrum information is as follows：1HNMR(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 poly- breast of hydridization that obtained product represents for structure above really
Acid.
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 caprolactone, intermediate product and stannous iso caprylate in mass ratio 20:1:1 weighs, N2Under atmosphere, 120 DEG C melt
Melt reaction 24h, a kind of hydridization polycaprolactone is obtained after filtering, washing, drying, it is as follows.Utilize NMR, FTIR, GPC and DSC
Structure to gained hydridization polycaprolactone is characterized with hot property, as a result as follows：Mn=12000g/mol；Tm=51 DEG C.
Nucleus magnetic hydrogen spectrum information is as follows：1H NMR(400MHz,DMSO)δ8.87(s,1H),5.45(s,1H),4.21-4.08
(m, 2H), 3.35 (s, 2H), 2.25 (m, 105H), 1.57-1.28 (m, 420H), it was demonstrated that obtained product is said structure really
The hydridization polycaprolactone that formula is represented.
Embodiment 5
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 48h, obtains
White suspension, a kind of hydridization PLA is obtained after centrifugation, washing, drying, as follows.Utilize NMR, FTIR, GPC and DSC
Structure to gained hydridization PLA is characterized with hot property, as a result as follows：Mn=63000g/mol；Tg=54 DEG C；Tm=
164℃。
Nucleus magnetic hydrogen spectrum information is as follows：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 obtain
The hydridization PLA that product represents for structure above really.
Embodiment 6
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, a kind of hydridization PLA is obtained after centrifugation, washing, drying, as follows.Utilize NMR, FTIR, GPC and DSC
Structure to gained hydridization PLA is characterized with hot property, as a result as follows：Mn=12000g/mol；Tg=46 DEG C；Tm=
156℃。
Nucleus magnetic hydrogen spectrum information is as follows：1HNMR(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 production
The hydridization PLA that thing represents for structure above really.
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, it is as follows.Using NMR, FTIR, GPC and DSC to the structure of gained hydridization PLA with
Hot property is characterized, Mn=13000g/mol；Tg=44 DEG C；Tm=154 DEG C.
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, monoethanolamine, ethylenediamine, hexamethylene diamine, tetrahydrofuran used etc. are Chinese medicines group chemical reagent
Co., Ltd's product, is analyzed pure.
It is from 0 DEG C of speed liter with 10 DEG C/min by hydridization type polyester that above-mentioned differential scanning calorimeter (DSC), which characterizes step,
Temperature tests polyester fiberglass transition temperature (T to more than melting point polyester 30 DEG Cg) and fusing point (Tm), number-average molecular weight (Mn) pass through height
Effect liquid phase chromatogram (GPC) is measured.
The specific method of testing that 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 feature of the not be the same as Example compound of table 1
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 hydridization type polyester, it is characterised in that the hydridization type polyester has the architectural feature of (I) or (II)：
；
Wherein, R1、R2For the polyester segment of carbon number 40 ~ 2300；
P is the integer between 1 ~ 9.
2. hydridization type polyester according to claim 1, it is characterised in that the R1And R2It is identical or different.
3. hydridization type polyester according to claim 1, it is characterised in that the internal ester monomer of the polyester segment is the third friendship
At least one of ester, butyrolactone, valerolactone, caprolactone, caprylolactone.
4. the preparation method of the hydridization type polyester described in a kind of claim 1, it is characterised in that methods described is to use scheme N systems
It is for architectural feature（I）Hydridization type polyester, or be characterized as with scheme M preparation structures（II）Hydridization type polyester；
Wherein, scheme N includes following preparation process：
（1）By diethyl oxalate and monoethanolamine reaction synthesis terminal hydroxy group intermediate product A, chemical constitution is (III)：
(III)；
（2）Trigger internal ester monomer polymerization using intermediate product A, obtain a kind of hydridization type polyester, chemical constitution is (I)：
(I)；
Wherein, R1、R2For the polyester segment of carbon number 40 ~ 2300；P is the integer between 1 ~ 9；
Wherein, scheme M includes following preparation process：
（a）By diethyl oxalate and diamine compound reaction synthetic mesophase product B, chemical constitution is (IV)：
(IV)；
（b）By intermediate product B and monoethanolamine reaction synthesis terminal hydroxy group intermediate product C, chemical constitution is (V)：
(V)；
（c）Trigger internal ester monomer polymerization using intermediate product C, obtain a kind of hydridization type polyester, chemical constitution is (II)：
(II)；
Wherein, R1、R2For the polyester segment of carbon number 40 ~ 2300；P is the integer between 1 ~ 9.
5. the preparation method of a kind of hydridization type polyester according to claim 4, it is characterised in that the internal ester monomer is third
At least one of lactide, butyrolactone, valerolactone, caprolactone, caprylolactone.
6. according to a kind of preparation method of any described hydridization type polyester of claim 4 ~ 5, it is characterised in that the diamine
Compound be ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, certain herbaceous plants with big flowers diamines, hendecane diamines, dodecamethylene diamine, tetradecane diamines,
Any one in octadecamethylene diamine.
7. according to a kind of preparation method of any described hydridization type polyester of claim 4 ~ 5, it is characterised in that in the initiation
The reaction of ester monomer polymerization is carried out under the catalysis of stannous octoate or stannous iso caprylate.
8. the application of hydridization type polyester described in claim 1.
9. application according to claim 8, it is characterised in that be to be applied to plastic material technical field.
10. application according to claim 8, it is characterised in that be used to packing, weave, medical treatment consumptive materials, disposable plastic
Product or agriculture field.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110483320A (en) * | 2019-09-10 | 2019-11-22 | 山西省化工研究所（有限公司） | A method of double-Oxoacetic Acid esters compound is synthesized using alcohols solvent |
| CN112094401A (en) * | 2020-09-27 | 2020-12-18 | 江南大学 | Degradable polyester and preparation method and application thereof |
| CN115322539A (en) * | 2022-06-27 | 2022-11-11 | 广东春夏新材料科技股份有限公司 | Polylactic acid composite material and preparation method thereof |
| CN116332866A (en) * | 2023-03-02 | 2023-06-27 | 浙江大学 | Preparation method of 2,2' -bis (2-oxazoline) |
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| CN105585588A (en) * | 2015-12-29 | 2016-05-18 | 北京航空航天大学 | Carborane-containing organic matter, PET (polyethylene terephthalate) as neutron radiation protection material as well as preparation thereof |
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| CN102869696A (en) * | 2010-04-29 | 2013-01-09 | 陶氏环球技术有限责任公司 | Hybrid polyester-polyether polyols |
| CN103205203A (en) * | 2013-01-15 | 2013-07-17 | 浙江鹏孚隆科技有限公司 | Nanometer SiO2 hybrid polyester modified organosilicon non-stick paint and coating method thereof |
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| CN107189049B (en) | 2019-03-01 |
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