CN109503817A - A kind of poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability and preparation method thereof - Google Patents
A kind of poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability and preparation method thereof Download PDFInfo
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- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- C08G63/82—Preparation processes characterised by the catalyst used
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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Abstract
The present invention provides poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) esters of a kind of biological degradability and preparation method thereof, the preparation method is using cheap bio-based materials --- oxalic acid, succinic acid and ethylene glycol are raw material, esterification occurs under higher esterification temperature (180 ~ 200 DEG C), obtain the more aggressiveness with end group oxalic acid glycol ester hydroxyl, then in 220 ~ 230 DEG C of generation melt polycondensations, poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability of high molecular weight is prepared, the oxalic acid aqueous solution of 0.05 ~ 0.3g/mL has been obtained simultaneously, it can be used as byproduct and directly uses, or it removes water and continues to use as raw material.Preparation method of the invention not only increases the rate of polycondensation reaction, and polymerization reaction time is greatly shortened, and has obtained the polyester of high molecular weight, the intrinsic viscosity of product is high, and color is good, and crystalline rate is fast, the machine-shaping property for improving copolyesters is conducive to the production of material.
Description
Technical field
The present invention relates to a kind of biodegradable copolyesters and preparation method thereof, and in particular to a kind of biological degradability is poly-
(succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester and preparation method thereof.
Background technique
Polyethylene glycol succinate (PES) is a kind of semicrystalline aliphatic polyester, and glass transition temperature is about -10
DEG C, fusing point is about 102 DEG C, is higher melting-point a kind of polymer in aliphatic polyester, is only second to poly butylene succinate
(PBS), biodegradation rate is greater than PBS.The PES of high molecular weight has strong with mechanics similar in low density polyethylene (LDPE) and polypropylene
Degree can replace general-purpose plastics directly to use.PES is cheap, fusing point is high, biodegradability is good, great exploitation potential.
The synthetic method of PES mainly has solution polycondensation, polycondensation chain extension method and direct polycondensation method.
Solution polycondensation can synthesize the PES of higher relative molecular weight, and still, reaction speed is slower, need to solvent
Recovery processing, high production cost, it is difficult to obtain practical application.Sun Jie etc. is synthesized using decahydronaphthalene as solvent by polymerisation in solution
The PES of high relative molecular weight,M n=49000,M w =127000, but its polycondensation reaction time is 12 ~ 14h.
Polycondensation chain extension method be it is a kind of can be under relatively mild operating condition, the high relative molecular mass of synthesis in the short period
The method of PES.CN101628972 discloses a kind of preparation method of polyethylene glycol succinate, is with succinic acid, ethylene glycol
For raw material, high boiling solvent is added, finally removes solvent again, oligomer is obtained, then with diisocyanate, binary acyl chlorides or two
First acid anhydrides is chain extender, prepares the polyester that number-average molecular weight is up to 200,000 or more.But due to chain extender used (such as
Diisocyanate etc.) toxicity it is very big, need its dosage of strict control to reduce its residual in the product, and purifying process is multiple
It is miscellaneous, inconvenience is brought to actual production.
The equipment and technique of direct polycondensation method are relatively simple, but it is needed with Sb2O3With GeO2As catalyst.Sb2O3
It is easy to decompose, and additional amount is more, so that product colour is deeper；GeO2Valuableness is unsuitable for industrializing.
Due to the synthetic method of PES or the reaction time is too long or complex process or higher cost, is unsuitable for
Industrial-scale production, high molecular weight PES product is current and industrialization is not implemented.In addition, the PES product that prepared by existing method
Crystalline rate is too low, is unfavorable for processing and forming, and then also limits the development of PES.Therefore, it develops one kind and quickly prepares macromolecule
The method for measuring PES, and make PES product that there is highly crystalline rate, while not improving cost, industry and academia are constantly pursued
Target.
Summary of the invention
It is an object of the invention to provide a kind of poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability and
Preparation method improves the crystalline rate and machine-shaping property of product to shorten polymerization reaction time.
The object of the present invention is achieved like this:
A kind of poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability, shown in molecular chain structure such as formula (I):
(I)
In formula, x is the degree of polymerization of poly- oxalic acid glycol ester in repetitive structure, and y is polyethylene glycol succinate in repetitive structure
The degree of polymerization, n represent repetitive structure number, nx=0 ~ 2, ny=120 ~ 200；
End group A and end group B is selected from any one in EOX, EBS, and end group A and end group B are identical or different；
EOX is, EBS is,
And in poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester, two kinds of terminal number ratios
；
It is calculated according to nucleus magnetic hydrogen spectrum after purification, the number-average molecular weight of the ester isM n = 1.7×104~3.0×104, intrinsic viscosity
[η]>0.9。
The preparation method of poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability of the invention includes following
Step:
(1) raw material, catalyst and antioxidant are added in reaction kettle, the raw material is that succinic acid, oxalic acid and ethylene glycol are massaged
The mixture that you mix than 23: m: n, wherein 2.40≤m < 5.34, n=1.2 (23+m)；The catalyst be butyl titanate,
The mixture of zinc acetate and antimony oxide, the antioxidant are triphenyl phosphate；
(2) synthesis under normal pressure, reaction temperature are 180 ~ 200 DEG C under nitrogen protection；
(3) 220 ~ 230 DEG C are warming up to, 50 ~ 100Pa is decompressed to, the reaction was continued；
(4) after reaction, nitrogen protection bottom discharge, and be cooled to room temperature to get poly- (the succinic acid second two of biological degradability is arrived
Alcohol-co- oxalic acid ethylene glycol) ester.
In the step (1), the molar ratio of succinic acid, oxalic acid and ethylene glycol is 23:3.9:32.3.
In the step (1), the butyl titanate dosage is 0.5 ~ 1wt ‰, preferably 1wt ‰；Triphenyl phosphate is used
Amount is 1-2 wt ‰, preferably 1.5wt ‰；The mass ratio of butyl titanate, zinc acetate and antimony oxide is preferably 1: 3: 1.
In the step (2), the reaction time is 3 ~ 4h, preferably 3.5h.
In the step (3), the reaction time is 3 ~ 6h, preferably 4.5h.
The present invention uses cheap bio-based materials --- and oxalic acid, succinic acid and ethylene glycol is raw materials, in higher esterification
Esterification occurs at temperature (180 ~ 200 DEG C), obtains the more aggressiveness with end group oxalic acid glycol ester hydroxyl, then exists
220 ~ 230 DEG C of generation melt polycondensations, and consumption of oxalic acid is limited in particular range, the modified copolymer of high molecular weight is prepared
Ester.The oxalic acid aqueous solution of 0.05 ~ 0.3g/mL has been obtained simultaneously, byproduct has been can be used as and directly uses, or has removed water and continues
It is used as raw material.
Reaction mechanism of the invention are as follows:
Esterification obtains the m aggressiveness P with oxalic acid glycol ester hydroxyl end groupsmWith with EGS ethylene glycol succinate hydroxyl end groups
N aggressiveness Pn, PmAnd PnEster exchange reaction is carried out, a the or b carbonylic carbon atom on oxygen atom attack oxalic acid group on hydroxyl 2,
Form (m+n) aggressiveness Pm+n, reaction equation is as follows.
The crystallization mechanism of gained copolyesters of the invention:
In height-oriented melt gradually cooling procedure, different poly- oxalic acid glycol ester (PEOX) blocks are (main in copolyesters
The block in terminal sites) between can be spontaneous aggregation generation mutually separate, and in 80 DEG C of -130 DEG C of temperature ranges between crystallize；
When temperature, which continues, reduces and reach the crystallization temperature section of polyethylene glycol succinate (PES) block (20 DEG C -80 DEG C), PEOX
Crystal accelerates the crystallization of PES as heterogeneous nucleus, and crystallization process schematic diagram is shown in Fig. 7.
Preparation method of the invention not only increases the rate of polycondensation reaction, and polymerization reaction time is greatly shortened, and
And the polyester of high molecular weight has been obtained, the intrinsic viscosity of product is high, and crystalline rate is fast, improves the processing forming of copolyesters
Can, be conducive to the production and processing of material.
The dosage of the catalytic antimony trioxide is not more than 1wt ‰ in preparation method of the invention, and products obtained therefrom color is good.
Detailed description of the invention
Fig. 1 is the photo in kind of comparative example 1, copolyesters prepared by embodiment 1 and embodiment 2, and in figure, the left side is comparative example
1 copolyesters, centre are the copolyesters of embodiment 1, and the right is the copolyesters of embodiment 2.
Fig. 2 is copolyesters prepared by embodiment 1 and embodiment 21H NMR spectra, A represents embodiment 1 in figure, and B is represented
Embodiment 2.
Fig. 3 is the DSC heating curve of copolyesters.
Fig. 4 is the temperature lowering curve of copolyesters.
Fig. 5 is isothermal crystal curve of the copolyesters at 75 DEG C, and in figure, curve 0 represents comparative example, and curve 1 represents embodiment
1, curve 2 represents embodiment 2, and curve 3 represents embodiment 3.
Fig. 6 is the stress strain curve of copolyesters, and in figure, curve 0 represents comparative example, and curve 1 represents embodiment 1, and curve 2 represents
Embodiment 2, curve 3 represent embodiment 3.
Fig. 7 is the crystallization process schematic diagram of copolyesters.
Specific embodiment
Below with reference to embodiment, the present invention is further elaborated, the process being not described in detail in the following embodiments and
Method is conventional method well known in the art, and raw materials used or reagent is unless otherwise stated commercially available product in embodiment, can be led to
Commercial channel is crossed to buy.
Raw materials used pure to analyze in following embodiments, purity is 99%, and triphenyl phosphate, succinic acid are purchased in Mike
Lin company；Ethylene glycol is purchased in Aladdin company, and oxalic acid (containing two crystallizations water) is purchased in Tianjin North Star Founder chemical reagent work；Vinegar
Sour zinc is purchased in Tianjin Ke Miou chemical reagent development centre；Antimony oxide is purchased in three factory of Tianjin chemical reagent.
Embodiment 1
By reaction raw materials succinic acid 60.0g(0.508mol), oxalic acid (containing two crystallizations water) 6.7g(0.053mol), ethylene glycol
41.7g(0.673mol) and catalyst butyl titanate 0.067g, zinc acetate 0.200g, antimony oxide 0.067g and antioxygen
Agent triphenyl phosphate 0.100g is added in reaction kettle；Under nitrogen protection, 180 DEG C are heated to, starts stirring, under normal pressure
React 2h, nitrogen flow rate is 20 mL/min, after be warming up to 200 DEG C of reaction 1h, nitrogen flow rate is 100-200 mL/min；After rise
Temperature starts to be decompressed to 50-100Pa, reacts 1h to 220 DEG C；230 DEG C are finally warming up to, the reaction was continued at pressure 50-100Pa
5h, nitrogen protection discharging, and be cooled to room temperature, reactant yield 94%(contains relative to the theory for the formation PES that succinic acid is added
Amount, similarly hereinafter).
The PES copolyesters product of synthesis is just like flowering structure and property: 1) end group oxalic acid group content is 0.7mol%；2) outside
See faint yellow solid；3) inherent viscosity [η]=1.05；4) 102 DEG C of fusing point, crystallize 6 J.g of enthalpy change by 38 DEG C of crystallization temperature-1；5) it draws
Stretching intensity is 50 ± 2 MPa, and elongation rate of tensile failure is 1380 ± 110%.
Embodiment 2
By reaction raw materials succinic acid 60.0g(0.508mol), oxalic acid (containing two crystallizations water) 10.3g(0.081mol), ethylene glycol
43.8g(0.707mol) and catalyst butyl titanate 0.070g, zinc acetate 0.211g, antimony oxide 0.070g and antioxygen
Agent triphenyl phosphate 0.105g is added in reaction kettle；Under nitrogen protection, 180 DEG C are heated to, starts stirring, under normal pressure
React 2h, nitrogen flow rate is 20 mL/min, after be warming up to 200 DEG C of reaction 1h, nitrogen flow rate is 100-200 mL/min；After rise
Temperature starts to be decompressed to 50-100Pa, reacts 1h to 220 DEG C；230 DEG C are finally warming up to, the reaction was continued at pressure 50-100Pa
4.5h, nitrogen protection discharging, and be cooled to room temperature, reactant yield 98%.
The PES copolyesters product of synthesis is just like flowering structure and property: 1) end group oxalic acid group content is 2.3mol%；2) outside
See faint yellow solid；3) inherent viscosity [η]=1.15；4) 104 DEG C of fusing point, crystallize enthalpy change 16J.g by 44 DEG C of crystallization temperature-1；5) it draws
Stretching intensity is 48 ± 2MPa, and elongation rate of tensile failure % is 1050 ± 110.
Embodiment 3
By reaction raw materials succinic acid 60.0g(0.508mol), oxalic acid (containing two crystallizations water) 10.9g(0.086mol), ethylene glycol
44.2g(0.713mol) and catalyst butyl titanate 0.071g, zinc acetate 0.214g, antimony oxide 0.071g and antioxygen
Agent triphenyl phosphate 0.106g is added in reaction kettle；Under nitrogen protection, 180 DEG C are heated to, starts stirring, under normal pressure
React 2.5h, nitrogen flow rate is 20 mL/min, after be warming up to 200 DEG C of reaction 1h, nitrogen flow rate is 100-200 mL/min；Afterwards
220 DEG C are warming up to, starts to be decompressed to 50-100Pa, reacts 2h；230 DEG C are finally warming up to, is continued at pressure 50-100Pa anti-
2.5h, nitrogen protection discharging are answered, and is cooled to room temperature, reactant yield 98%.
The PES copolyesters product of synthesis is just like flowering structure and property: 1) end group oxalic acid group content is 3.3 mol %；2)
Appearance nitrogen yellow solid；3) inherent viscosity is [η]=0.98；4) 105 DEG C of fusing point, crystallize 45 J.g of enthalpy change by 47 DEG C of crystallization temperature-1；
5) tensile strength is 48 ± 2MPa, and elongation rate of tensile failure % is 960 ± 85.
Embodiment 4
By reaction raw materials succinic acid 60.0g(0.508mol), oxalic acid (containing two crystallizations water) 11.4g(0.090mol), ethylene glycol
44.5g(0.718mol) and catalyst butyl titanate 0.071g, zinc acetate 0.214g, antimony oxide 0.071g and antioxygen
Agent triphenyl phosphate 0.107g is added in reaction kettle；Under nitrogen protection, 180 DEG C are heated to, starts stirring, under normal pressure
React 2.5h, nitrogen flow rate is 20 mL/min, after be warming up to 200 DEG C of reaction 1h, nitrogen flow rate is 100-200 mL/min；Afterwards
220 DEG C are warming up to, starts to be decompressed to 50-100Pa, reacts 2h；230 DEG C are finally warming up to, is continued at pressure 50-100Pa anti-
2.5h, nitrogen protection discharging are answered, and is cooled to room temperature, reactant yield 98%.
The PES copolyesters product of synthesis is just like flowering structure and property: 1) end group oxalic acid group content is 3.8 mol %；2)
Appearance nitrogen yellow solid；3) inherent viscosity is [η]=0.96；4) 105 DEG C of fusing point, crystallize enthalpy change 45 by 47 DEG C and 60 DEG C of crystallization temperature
J.g-1；5) tensile strength is (48 ± 2) MPa, and elongation rate of tensile failure is (1050 ± 110) %.
Embodiment 5
By reaction raw materials succinic acid 60.0g(0.508mol), oxalic acid (containing two crystallizations water) 12g(0.095mol), ethylene glycol
44.9g(0.724mol) and catalyst butyl titanate 0.072g, zinc acetate 0.216g, antimony oxide 0.072g and antioxygen
Agent triphenyl phosphate 0.108g is added in reaction kettle；Under nitrogen protection, 180 DEG C are heated to, starts stirring, under normal pressure
React 2.5h, nitrogen flow rate is 20 mL/min, after be warming up to 200 DEG C of reaction 1h, nitrogen flow rate is 100 ~ 200 mL/min；Afterwards
220 DEG C are warming up to, starts to be decompressed to 50-100Pa, reacts 2h；230 DEG C are finally warming up to, is continued at pressure 50-100Pa anti-
2.5h, nitrogen protection discharging are answered, and is cooled to room temperature, reactant yield 98%.
The PES copolyesters product of synthesis is just like flowering structure and property: 1) end group oxalic acid group content is 4.0 mol %；2)
Appearance nitrogen yellow solid；3) inherent viscosity is [η]=0.94；4) 105 DEG C of fusing point, crystallize 35 J.g of enthalpy change by 60 DEG C of crystallization temperature-1；
5) tensile strength is 43 ± 2MPa, and elongation rate of tensile failure % is 1130 ± 110.
Embodiment 6
By reaction raw materials succinic acid 60.0g(0.508mol), oxalic acid (containing two crystallizations water) 15.0g(0.118mol), ethylene glycol
46.6g(0.751mol) and catalyst butyl titanate 0.075g, zinc acetate 0.225g, antimony oxide 0.075g and antioxygen
Agent triphenyl phosphate 0.112g is added in reaction kettle；Under nitrogen protection, 180 DEG C are heated to, starts stirring, under normal pressure
React 3h, nitrogen flow rate is 20 mL/min, after be warming up to 200 DEG C of reaction 1h, nitrogen flow rate is 100 ~ 200 mL/min；After rise
Temperature starts to be decompressed to 50-100Pa, reacts 2h to 220 DEG C；230 DEG C are finally warming up to, the reaction was continued at pressure 50-100Pa
4h, nitrogen protection discharging, and be cooled to room temperature, reactant yield 102%.
The PES copolyesters product of synthesis is just like flowering structure and property: 1) end group oxalic acid group content is 4.3 mol %；2)
Appearance nitrogen yellow solid；3) inherent viscosity is [η]=0.91；4) 101 DEG C of fusing point, crystallize 16 J.g of enthalpy change by 42 DEG C of crystallization temperature-1；
5) tensile strength is 34 ± 1MPa, and elongation rate of tensile failure % is 750 ± 50.
Embodiment 7
By reaction raw materials succinic acid 60.0g(0.508mol), oxalic acid (containing two crystallizations water) 6.0g(0.0474mol), ethylene glycol
41.3g(0.666mol) and catalyst butyl titanate 0.066g, zinc acetate 0.198g, antimony oxide 0.066g and antioxygen
Agent triphenyl phosphate 0.099g is added in reaction kettle；Under nitrogen protection, 180 DEG C are heated to, starts stirring, under normal pressure
React 3h, nitrogen flow rate is 20 mL/min, after be warming up to 200 DEG C of reaction 1h, nitrogen flow rate is 100 ~ 200 mL/min；After rise
Temperature starts to be decompressed to 50-100Pa, reacts 2h to 220 DEG C；230 DEG C are finally warming up to, the reaction was continued at pressure 50-100Pa
6h fails to reach pole-climbing (determining the phenomenon that reaction terminates) nitrogen protection discharging, and is cooled to room temperature, and copolyesters color is deep yellow.
Embodiment 8
By reaction raw materials succinic acid 60.0g(0.508mol), oxalic acid (containing two crystallizations water) 17.0g(0.134mol), ethylene glycol
47.8g(0.771mol) and catalyst butyl titanate 0.077g, zinc acetate 0.231g, antimony oxide 0.077g and antioxygen
Agent triphenyl phosphate 0.116g is added in reaction kettle；Under nitrogen protection, 180 DEG C are heated to, starts stirring, under normal pressure
React 3h, nitrogen flow rate is 20 mL/min, after be warming up to 200 DEG C of reaction 1h, nitrogen flow rate is 100 ~ 200 mL/min；After rise
Temperature starts to be decompressed to 50-100Pa, reacts 2h to 220 DEG C；230 DEG C are finally warming up to, the reaction was continued at pressure 50-100Pa
6h fails to reach pole-climbing (determining the phenomenon that reaction terminates) nitrogen protection discharging, and is cooled to room temperature, and copolyesters color is deep yellow,
And yield is 89%, it is lower.
Comparative example 1
By reaction raw materials succinic acid 60.0g(0.508mol), ethylene glycol 40.9g(0.660mol) and the catalytic antimony trioxide
0.24g and antioxidant triphenyl phosphate 0.18g is added in reaction kettle；Under nitrogen protection, 180 DEG C are heated to, is started
Stirring, reacts 2h under normal pressure, after be warming up to 200 DEG C of reaction 1h, nitrogen flow rate is 20 mL/min；After be warming up to 230 DEG C, open
Beginning is decompressed to 50 ~ 100Pa, the reaction was continued 5h, nitrogen protection discharging, and is cooled to room temperature, reactant yield 96%.
The PES product of synthesis is just like flowering structure and property: 1) appearance dark yellow solid；2) inherent viscosity [η]=0.92；3)
103 DEG C of fusing point, 40 DEG C of crystallization temperature, crystallize enthalpy change 3J.g-1；4) tensile strength be 44 ± 2MPa, elongation rate of tensile failure be 850 ±
80%。
Structural characterization and performance test are carried out to products obtained therefrom.Note: sample used in the measurement of inherent viscosity passes through chloroform
It is repeated multiple times to remove small molecule after dissolution, and with a large amount of methanol extractions；The sample of other tests does not purify.
Nucleus magnetic hydrogen spectrum characterization: using AvIII type nuclear magnetic resonance chemical analyser (600 MHz, Bruker BioSpin Co.,
Germany) with deuterated chloroform (CDCl3) it is solvent, TMS is internal standard, the core of copolyesters prepared by measurement embodiment 1, embodiment 2
Magnetic hydrogen spectrum (1H NMR), as a result see Fig. 2.
From the point of view of Fig. 2, d and c(b+c+e+f) place represent hydrogen area it is almost equal, it can be deduced that on polymer backbone
The content of ethylene glycol and the content of succinic acid almost, illustrate that almost all is PES segment, oxalic acid unit on polymer backbone
Hardly on skeleton, that is, the PEOX segment overwhelming majority is in terminal sites.
In addition, the spectrogram of 2 products obtained therefrom of comparative example 1 and embodiment, with the increase (embodiment 2 of oxalic acid additional amount
Oxalic acid additional amount be greater than the oxalic acid additional amount of embodiment 1), a and g locate the area ratio increase of represented hydrogen, i.e. product end group is careless
The molar ratio of sour glycol ester group and EGS ethylene glycol succinate end moieties increases, and corresponding polycondensation reaction time shortens.Add
Lower than lower border value or when being higher than upper boundary values, the reaction time can extend the oxalic acid amount entered, cannot get high molecular weight in 6h
Polymer.
The measurement of intrinsic viscosity [η]: using Ubbelohde viscometer (DC9V/0, Schott Co., Germany) to implementation
Copolyesters prepared by example 1 ~ 6 and comparative example 1 carries out characteristic viscosity measuring, and the chloroformic solution that copolymerization ester concentration is 0.01 g/mL is surveyed
Trying temperature is (25 ± 0.1) DEG C, and test result is shown in Table 1.
Fusion-crystallization behavior characterization: differential scanning calorimetry (DSC) instrument (U.S., Perkine-Elmer are used
DSC8000) melt and crystallization behavior of copolyesters prepared by embodiment 1 ~ 6 and comparative example 1 is characterized.The weight of sample is about
It is 5 milligrams.First with the heating rate of 60 DEG C/min, by copolyesters from room temperature to 130 DEG C, then with 60 DEG C/min's
Rate of temperature fall is cooled to -30 DEG C, eliminates heating power history, is then warming up to 130 DEG C with the heating rate of 10 DEG C/min and obtains sample
Heating curve, as shown in Figure 3；Then -30 DEG C are cooled to the heating rate of 10 DEG C/min and obtain the temperature lowering curve of sample, such as schemed
Shown in 4；In triplicate by the program, 75 DEG C then are down to the rate of temperature fall of 10 DEG C/min, 75 DEG C of maintenance is constant, until sample
Crystallization terminates, and obtains the isothermal crystal curve of embodiment 1 ~ 3 Yu comparative example, as shown in Figure 5；Crystallization temperature and crystallization enthalpy change
It is shown in Table 1.
As shown in Figure 4, on the DSC curve of each sample, comparative example is hardly visible peak crystallization, and embodiment 1-6 can be observed
To apparent peak crystallization (Tc), this explanation compared with comparative example, contains the poly- oxalic acid ethylene glycol block of end group in melt cooling
Embodiment 1-6 is easier to crystallize.
As shown in Figure 5, at 75 DEG C, comparative example is completed to need time about 55min to crystallization from crystallization is started, and embodiment 1 needs
Offer 40min, embodiment 2 need about 20min, and embodiment 3 about needs most short the time required to 8min(crystallization), embodiment 1-3 is complete
It is gradually shortened at the time of crystallization, illustrates that the crystalline rate of copolyesters is gradually increased.
Characterization of Tensile: 140 DEG C of injection temperature, 25 DEG C of film-forming temperature, by 1 institute of embodiment 1, embodiment 2 and comparative example
It prepares copolyesters and is fabricated to standard dog bone batten.With universal testing machine according to the draftability of GB/T-1040-2006 test material
Can, it is measured using 1BA sample, rate of extension 25mm/min, 5 battens of each sample test are averaged.Gained is drawn
Curve is stretched as shown in fig. 6, tensile strength and tensile elongation are shown in Table 1.
Table 1: properties of product list
Claims (9)
1. a kind of poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability, which is characterized in that its molecular chain structure
As shown in formula (I):
(I)
In formula, x is the degree of polymerization of poly- oxalic acid glycol ester in repetitive structure, and y is polyethylene glycol succinate in repetitive structure
The degree of polymerization, n represent repetitive structure number, nx=0 ~ 2, ny=120 ~ 200；
A and B is selected from any one in EOX, EBS, and A is identical or different with B；
EOX is, EBS is。
2. poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability according to claim 1, feature exist
In, in poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester, the ratio between two kinds of terminal numbers
。
3. a kind of preparation side of poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability described in claim 1
Method, which comprises the following steps: raw material, catalyst and antioxidant are added in reaction kettle, through esterification, melt
Melt polycondensation to get poly- (succinic acid ethylene glycol-co- oxalic acid ethylene glycol) ester of biological degradability；The raw material be succinic acid, oxalic acid with
The mixture of ethylene glycol 23: m: n mixing in molar ratio, wherein 2.4≤m < 5.34, n=1.2 (23+m).
4. preparation method according to claim 3, which is characterized in that the molar ratio of succinic acid, oxalic acid and ethylene glycol is 23:
3.9:32.3。
5. preparation method according to claim 3, which is characterized in that the catalyst be butyl titanate, zinc acetate and
The mixture of antimony oxide, the butyl titanate dosage are 0.5 ~ 1wt ‰ of succinic acid and total oxalate.
6. preparation method according to claim 5, which is characterized in that butyl titanate, zinc acetate and antimony oxide
Mass ratio is 1: 3: 1.
7. preparation method according to claim 3, which is characterized in that the antioxidant is triphenyl phosphate, phosphoric acid triphen
Ester dosage is the 1-2 wt ‰ of succinic acid and total oxalate.
8. preparation method according to claim 3, which is characterized in that esterification is synthesis under normal pressure under nitrogen protection,
Reaction temperature is 180 ~ 200 DEG C, and the reaction time is 3 ~ 4h.
9. preparation method according to claim 3, which is characterized in that the temperature of melt polycondensation is 220 ~ 230 DEG C, and pressure is
50 ~ 100Pa, reaction time are 3 ~ 6h.
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