CN109320699A - A kind of thermoplastic aliphatic-aromatic copolyester ester elastomer and preparation method thereof - Google Patents
A kind of thermoplastic aliphatic-aromatic copolyester ester elastomer and preparation method thereof Download PDFInfo
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- CN109320699A CN109320699A CN201811047949.1A CN201811047949A CN109320699A CN 109320699 A CN109320699 A CN 109320699A CN 201811047949 A CN201811047949 A CN 201811047949A CN 109320699 A CN109320699 A CN 109320699A
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- acid
- aliphatic
- aromatic copolyester
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- oxydibenzoic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/78—Preparation processes
Abstract
The invention belongs to the synthesis technical fields of random copolymerization ester elastomer, and in particular to a kind of thermoplastic aliphatic-aromatic copolyester ester elastomer and preparation method thereof.Using 1,4-butanediol, aliphatic dibasic acid and oxydibenzoic acid or oxydibenzoic acid dimethyl ester as raw material, copolyesters is prepared using the polymerization for being first esterified aftercondensated.The present invention can be used general polyester synthesis device and polymerize, and successive reaction is carried out in a manner of disposably feeding intake, easy to operate, easy to industrialized production.Copolyesters prepared by the present invention has good toughness and resilience；The linear structure of copolyesters assigns the good processing performance of material simultaneously.Therefore, the present invention prepares the simple process of copolyesters, which has broad application prospects in terms of thermoplastic biologically degradable elastomer.
Description
Technical field
The invention belongs to the synthesis technical fields of random copolymerization ester elastomer, and in particular to a kind of thermoplastic aliphatic-virtue
Fragrant race's copolyester elastomer and preparation method thereof.
Background technique
Thermoplastic polyester elastomer is a kind of novel high polymer material for having both rubber and plastic properties, with its excellent property
It can favor with workability by people.Currently, thermoplastic polyester elastomer is mainly A-B type block polymer material.Wherein,
Using armorphous polyester or polyethers as soft segment, crystal type or aromatic polyester are hard block.Two-step method is generallyd use that is, first preparing
Soft segment and hard section performed polymer, then chain extender is used to react with hard section, soft segment to form block structure.
If patent CN 101768246B is disclosed, terminal hydroxy group aliphatic polyester and terminal hydroxy group aromatic polyester are first prepared, so
Afterwards using diisocyanate as chain extender, a kind of multi-block copolyesters are prepared for, the tensile strength for measuring the copolyesters is 10-
67MPa, elongation at break 20-1080%.104610522 B of patent CN is reported, by (the terminal hydroxy group poly-succinic of prepolymer I
Propylene glycol ester) and prepolymer II (terminal hydroxy group aromatic polyester or another terminal hydroxy group aliphatic polyester) is under inert gas protection
Heating melting stirs evenly, and diisocyanate is then added, and prepares high tenacity multiblock ester elastomer, elongation at break
For 1112-2200%.
Block copolyester elastomer is prepared relative to two-step method, it is then relatively simple that one-step method prepares random copolymerization ester elastomer
It is single, it is easier to industrialized production.One-step method is to put into reaction monomers in reactor in a manner of disposably feeding to connect
Continuous formula reaction, operating procedure are simple.So, in order to assign the soft chain segment and hard segment on random copolymerization ester structure, the present inventor
It was found that using 1,4-butanediol as glycol monomer, aliphatic dibasic acid and oxydibenzoic acid or oxydibenzoic acid dimethyl ester
Monomer has good toughness and resilience as comonomer, prepared atactic polyester.This is because binary aliphatic
The segment that acid monomers are formed has certain flexibility；Benzene in oxydibenzoic acid or oxydibenzoic acid dimethyl ester monomer structure
Ring is rigid structure, and ehter bond is then good flexible structure.As patent CN102558519A discloses a kind of liquid crystal high score
Sub- material declines chain rigidity it is pointed out that 4,4- oxydibenzoic acids contain ehter bond, thus the toughness of LCP or impact are strong
Degree increases.This ad hoc meter is using binary aliphatic acid monomers and oxydibenzoic acid or oxydibenzoic acid dimethyl ester list
Body, using the comprehensive function on flexible unit and rigid unitary structure, impart copolyesters still has well under random sequence
Toughness and resilience.
Summary of the invention
It is concentrated in the synthesis of blocked copolyester for the existing method for preparing polyester elastomer, method is generally two steps
Method, it is relative complex.An object of the present invention is to provide a kind of simple system of thermoplastic aliphatic-aromatic copolyester ester elastomer
Thermoplastic aliphatic made from Preparation Method and this method-aromatic copolyester ester elastomer.
The second object of the present invention is to use oxydibenzoic acid or oxydibenzoic acid diformazan from the angle of MOLECULE DESIGN
Ester assigns the good toughness of aliphatic-aromatic copolyester and rebound characteristics, and this hair as special aromatic comonomer
Bright thermoplastic aliphatic-aromatic copolyester ester elastomer weight average molecular weight is 20000-50000g/mol, elongation at break
For 800-1960%.
The present invention realizes that the technical solution of purpose is:
A kind of thermoplastic aliphatic-aromatic copolyester ester elastomer, chemical structural formula general formula are as follows:
In formula, x=1 or 4.
A kind of synthetic route of thermoplastic aliphatic-aromatic copolyester ester elastomer is as follows:
In formula, x=1 or 4.
It follows the steps below:
(1) band is added in 1,4- butanediol, aliphatic dibasic acid and oxydibenzoic acid or oxydibenzoic acid dimethyl ester
In the reaction vessel for having agitating device, condensing unit, nitrogen protection device；Catalyst is added into reaction vessel, opens condensation
Water is passed through N2, after then heat temperature raising melts monomer completely and is sufficiently mixed uniformly, it is continuously heating to esterification reaction temperature,
Then constant temperature esterification reacts 3-4h under agitation, when the collecting amount of water is at least up to the 80% of theoretical value, it is believed that esterification
Reaction terminates.
(2) enter polycondensation phase after esterification, it is specific: to remove condensing unit, change into equipped with safety flack, wheat formula
The vacuum evacuation device of vacuum meter and oil pump is gradually heated to polycondensation reaction temperature, and constant temperature polycondensation reaction 3- under agitation
4h, while control system vacuum degree is 50-80Pa, product is collected after being cooled to room temperature after polycondensation reaction, by what is be collected into
Product is dissolved with chloroform, adds methanol, and sediment is collected by filtration after being sufficiently stirred, through dry obtained thermoplasticity fat
Race-aromatic copolyester ester elastomer.Be added methanol obtain copolyesters precipitating be all be dissolved in chloroform using polyester and impurity, and
Polyester does not dissolve in methanol, and impurity is dissolved in the dissolution characteristics of methanol, achievees the purpose that purify polyester.
In order to obtain better elasticity, it is preferred that aliphatic dibasic acid described in step (1) is succinic acid, decanedioic acid
In any one.
It advanced optimizes, oxydibenzoic acid (ester) described in step (1) is 4,4- oxydibenzoic acid, 4,4- bis-
Any one in phenylate dicarboxylic acid dimethyl ester.
In order to avoid thermoplastic aliphatic obtained-aromatic copolyester ester elastomer in suitable molecular weight ranges
Wastage of material advanced optimizes, in step (1) 1,4-butanediol and aliphatic dibasic acid and
The moles total number of oxydibenzoic acid or moles total number with aliphatic dibasic acid and oxydibenzoic acid dimethyl ester
The ratio between be 4:1.
Advanced optimize, in step (1) catalyst be stannous chloride, it is stannous octoate, zinc acetate, butyl titanate, right
Any one or a few in toluenesulfonic acid, the dosage of catalyst are the moles total number of aliphatic dibasic acid and oxydibenzoic acid
Or the 0.5%-1.0% of the moles total number of aliphatic dibasic acid and oxydibenzoic acid dimethyl ester.
Synthesized thermoplastic aliphatic-aromatic copolyester ester elastomer initial modulus (i.e. Young's modulus) in order to prevent
Very high, it is not the curvilinear characteristic of typical high-toughness material, and material shows one that obvious surrender, which occurs, in load-deformation curve
As plastics characteristic (Qiang Erren), rather than the characteristic of high resilient material.Preferably, binary aliphatic described in step (1)
The ratio between mole and oxydibenzoic acid or the mole of oxydibenzoic acid dimethyl ester of acid are 40:60-70:30.
It advanced optimizes, esterification reaction temperature described in step (1) is 180 DEG C；Polycondensation reaction temperature in step (2)
It is 220 DEG C.
Thermoplastic aliphatic-aromatic copolyester ester elastomer as described above can by design feature (containing aliphatic monomer)
Know, can be used for preparing macromolecular thermoplastic Biodegradable elastomer product.
Compared with the prior art, the invention has the following beneficial effects:
1) since preparation method provided by the invention is to use disposably to put into monomer in consersion unit to carry out continuously
Thermoplastic aliphatic-aromatic copolyester ester elastomer of high molecular weight, random copolymerization prepared by the mode of change reaction, operation letter
Single, process controllability is strong, thus is not only to prepare thermoplastic co-polymer ester elastomer to have expanded a kind of new method, and this method
It is easily achieved the industrialization of product.
2) since the present invention uses oxydibenzoic acid or oxydibenzoic acid dimethyl ester as special aromatic copolyester
Monomer assigns the good toughness of aliphatic-aromatic copolyester and rebound characteristics.
3) weight average molecular weight range of polyester of the present invention be 20000-50000g/mol, elongation at break be 800~
1960%.Since thermoplastic aliphatic provided by the invention-aromatic copolyester ester elastomer mechanics elasticity can pass through aliphatic
The proportion of binary acid and oxydibenzoic acid or oxydibenzoic acid dimethyl ester is adjusted, thus can get and meet different uses
It is required that copolyester elastomer, its application space can be further expanded.
Detailed description of the invention
Fig. 1 is thermoplastic aliphatic-aromatic copolyester ester elastomer stress-strain of 1-4 of embodiment of the present invention preparation
Curve；
Fig. 2 is that thermoplastic aliphatic-aromatic copolyester ester elastomer cyclic tension prepared by the embodiment of the present invention 2 is bent
Line；
Fig. 3 is to melt in thermoplastic aliphatic-aromatic copolyester ester elastomer DSC spectrogram of the preparation of the embodiment of the present invention 2
Melt curve；
Fig. 4 is thermoplastic aliphatic-aromatic copolyester ester elastomer DMA curve prepared by the embodiment of the present invention 2.
Specific embodiment
The present invention is described in further detail below with reference to embodiment:
Embodiment 1:
By acid-alcohol ratio 4:1 by 1,4- butanediol 0.48mol (43.26g), succinic acid 0.048mol (5.67g) and diphenyl ether
The 250ml three-necked flask for having agitating device, condensing unit, nitrogen protection device is added in dioctyl phthalate 0.072mol (18.59g)
In, wherein the molar ratio of succinic acid and oxydibenzoic acid is 40:60.Catalyst butyl titanate is added dropwise into three-necked flask,
Its dosage is 0.5% (0.204g) of sour mole.Condensed water is opened, N is passed through2, it is heated to 180 DEG C, it is complete to monomer
After thawing, carries out constant temperature and stir esterification 4h, when the collecting amount of water reaches the 80% of theoretical value, it is believed that esterification knot
Beam；
Enter polycondensation phase after esterification, removes condensing unit, change into equipped with safety flack, wheat formula vacuum meter and oil
The vacuum evacuation device of pump is gradually heated to 220 DEG C, sustained response 4h, while control system vacuum degree is 50-80Pa, and polycondensation is anti-
Product is collected after being cooled to room temperature after answering, and the product being collected into is dissolved with chloroform, adds methanol, is sufficiently stirred
Thermoplastic aliphatic-aromatic copolyester ester elastomer that filtration drying is purified afterwards.
Embodiment 2
By 1,4-butanediol 0.48mol (43.26g), succinic acid 0.06mol (7.09g) and oxydibenzoic acid dimethyl ester
0.06mol (17.17g) is added in the 250ml three-necked flask for having agitating device, condensing unit, nitrogen protection device, wherein fourth
The molar ratio of diacid and oxydibenzoic acid dimethyl ester is 50:50.Catalyst butyl titanate is added dropwise into three-necked flask, uses
Amount is 1.0% (0.4g) of sour mole.Condensed water is opened, N is passed through2, 180 DEG C are heated to, after monomer melts completely,
It carries out constant temperature and stirs esterification 3h, when the collecting amount of water reaches the 80% of theoretical value, it is believed that esterification terminates；
Enter polycondensation phase after esterification, removes condensing unit, change into equipped with safety flack, wheat formula vacuum meter and oil
The vacuum evacuation device of pump is gradually heated to 220 DEG C, sustained response 3h, while control system vacuum degree is 50-80Pa, and polycondensation is anti-
Product is collected after being cooled to room temperature after answering, and the product being collected into is dissolved with chloroform, adds methanol, is sufficiently stirred
Thermoplastic aliphatic-aromatic copolyester ester elastomer that filtration drying is purified afterwards.
Embodiment 3
By acid-alcohol ratio 4:1 by 1,4-butanediol 0.48mol (43.26g), decanedioic acid 0.072mol (14.56g) and diphenyl ether
The 250ml three-necked flask for having agitating device, condensing unit, nitrogen protection device is added in dioctyl phthalate 0.048mol (12.40g)
In, wherein the molar ratio of decanedioic acid and oxydibenzoic acid is 60:40.Catalyst butyl titanate is added dropwise into three-necked flask,
Its dosage is 0.5% (0.2g) of sour mole.Condensed water is opened, N is passed through2, 180 DEG C are heated to, is melted completely to monomer
After change, carries out constant temperature and stir esterification 4h, when the collecting amount of water reaches the 80% of theoretical value, it is believed that esterification terminates；
Enter polycondensation phase after esterification, removes condensing unit, change into equipped with safety flack, wheat formula vacuum meter and oil
The vacuum evacuation device of pump is gradually heated to 220 DEG C, sustained response 4h, and system vacuum degree is 50-80Pa, after polycondensation reaction
Product is collected after being cooled to room temperature, the product being collected into is dissolved with chloroform, adds methanol, is crossed and is filtered dry after being sufficiently stirred
The dry copolymer thermoplastic aliphatic-aromatic copolyester elastomer purified.
Embodiment 4
By acid-alcohol ratio 4:1 by 1,4-butanediol 0.48mol (43.26g), decanedioic acid 0.084mol (16.99g) and diphenyl ether
Dicarboxylic acid dimethyl ester 0.036mol (10.30g) is added with agitating device, condensing unit, tri- mouthfuls of 250ml of nitrogen protection device
In flask, wherein the molar ratio of decanedioic acid and oxydibenzoic acid dimethyl ester is 70:30.Catalyst Ti is added dropwise into three-necked flask
Sour four butyl esters, dosage are 0.5% (0.2g) of sour mole.Condensed water is opened, N is passed through2, 180 DEG C are heated to, to list
After body melts completely, carries out constant temperature and stir esterification 3h, when the collecting amount of water reaches the 80% of theoretical value, it is believed that esterification is anti-
It should terminate；
Enter polycondensation phase after esterification, removes condensing unit, change into equipped with safety flack, wheat formula vacuum meter and oil
The vacuum evacuation device of pump is gradually heated to 220 DEG C, sustained response 3h, while control system vacuum degree is 50-80Pa, and polycondensation is anti-
Product is collected after being cooled to room temperature after answering, and the product being collected into is dissolved with chloroform, adds methanol, is sufficiently stirred
Thermoplastic aliphatic-aromatic copolyester ester elastomer that filtration drying is purified afterwards.
Thermoplastic aliphatic-aromatic copolyester ester elastomer obtained in each embodiment is tested with the following method
And evaluation:
Break-draw: using the triumphant strength in Shenzhen 10 type electronic universal tester of WD-II according to GB/T 1040-1992 into
Row measurement, obtains the load-deformation curve of fracture process.
Cyclic tension: it is tested using the 10 type electronic universal tester of WD-II of the triumphant strength in Shenzhen, with rate of extension
50mm/min makes batten reach strain 200%, then so that batten is restored to former length with the speed of -50mm/min, forms a week
The circulation of phase successively carries out round-trip stretch until 10 circulations, obtain the load-deformation curve of cyclic tension.
Melting curve: being tested using the differential scanning calorimeter of the Q200 of TA company of the U.S., under nitrogen protection with
10 DEG C/min is warming up to 120 DEG C by -40 DEG C, and constant temperature melts 3min and eliminates thermal history, then is scanned with 10 DEG C/min cooling to room temperature,
Then with 10 DEG C/min heating scan to 120 DEG C, using second of heating curve as melting curve.
Dynamic mechanical analysis: using 8000 instrument of PE company DMA, and frequency of oscillation is 1.0Hz under stretch mode, and amplitude is
50 μm, Range of measuring temp is -90 DEG C to 60 DEG C, and 3 DEG C/min of heating rate obtains fissipation factor-temperature curve.
It is apparent from figure 1 that thermoplastic aliphatic-aromatic copolyester bullet of random copolymerization prepared by embodiment 1 to 4
Property body load-deformation curve there is no yield point, show as the elastomer properties of high tenacity, wherein embodiment 2 be decanedioic acid with
When the molar ratio of oxydibenzoic acid dimethyl ester is 50:50, copolyesters has maximum tensile strength and elongation at break.From figure
In 2, it is apparent that embodiment 2 prepare random copolymerization thermoplastic aliphatic-aromatic copolyester ester elastomer show as it is high-elastic
The recoverability of property., it is apparent that thermoplastic aliphatic-aromatic copolyester of random copolymerization prepared by embodiment 2 from Fig. 3
Elastomer does not have melting peak, shows as amorphous polymer., it is apparent that the thermoplastic of random copolymerization prepared by embodiment 2 from Fig. 4
Property aliphatic-aromatic copolyester elastomer glass transition temperature be 19.7 DEG C < room temperature (25 DEG C), so material is in room temperature
Under show good sub-chain motion ability, thus have good rebound characteristics.
Claims (8)
1. a kind of thermoplastic aliphatic-aromatic copolyester ester elastomer, it is characterised in that: the copolyester elastomer is Isosorbide-5-Nitrae-fourth
The random copolymer of diol monomer, binary aliphatic acid monomers and oxydibenzoic acid or oxydibenzoic acid diformazan ester monomer,
Its chemical structural formula general formula is as follows:
In formula, x=1 or 4；
The weight average molecular weight of the copolyester elastomer is 20000-50000g/mol, elongation at break 800-1960%.
2. thermoplastic aliphatic as described in claim 1-aromatic copolyester method for producing elastomers, it is characterised in that:
Described method includes following steps:
(1) band is added in monomer 1,4-butanediol, aliphatic dibasic acid and oxydibenzoic acid or oxydibenzoic acid dimethyl ester
In the reaction vessel for having agitating device, condensing unit, nitrogen protection device；Catalyst is added into reaction vessel, opens condensation
Water is simultaneously passed through N2, after then heat temperature raising melts monomer completely and is sufficiently mixed uniformly, it is continuously heating to esterification reaction temperature,
Then constant temperature esterification reacts 3-4h under agitation, when the collecting amount of water is at least up to the 80% of theoretical value, it is believed that esterification
Reaction terminates；
(2) after esterification, condensing unit is removed, changes the vacuum means equipped with safety flack, wheat formula vacuum meter and oil pump into
It sets, is gradually heated to polycondensation reaction temperature, and constant temperature polycondensation reaction 3-4h under agitation, while control system vacuum degree is
50-80Pa collects product after being cooled to room temperature after polycondensation reaction, and the product being collected into is dissolved with chloroform, then plus
Enter methanol, sediment is collected by filtration after being sufficiently stirred, through dry obtained thermoplastic aliphatic-aromatic copolyester ester elastomer.
3. thermoplastic aliphatic according to claim 2-aromatic copolyester method for producing elastomers, feature exist
In: aliphatic dibasic acid described in step (1) be succinic acid, any one in decanedioic acid.
4. thermoplastic aliphatic according to claim 2-aromatic copolyester method for producing elastomers, feature exist
In: in step (1) moles total number of the mole of 1,4-butanediol and aliphatic dibasic acid and oxydibenzoic acid or with fat
The ratio between moles total number of race's binary acid and oxydibenzoic acid dimethyl ester is 4:1.
5. thermoplastic aliphatic according to claim 2-aromatic copolyester method for producing elastomers, feature exist
In rubbing for: the mole of aliphatic dibasic acid described in step (1) and oxydibenzoic acid or oxydibenzoic acid dimethyl ester
The ratio between your amount is 40:60-70:30.
6. thermoplastic aliphatic according to claim 2-aromatic copolyester method for producing elastomers, feature exist
In: esterification reaction temperature described in step (1) is 180 DEG C；Polycondensation reaction temperature described in step (2) is 220 DEG C.
7. thermoplastic aliphatic according to claim 2-aromatic copolyester method for producing elastomers, feature exist
In: catalyst described in step (1) be stannous chloride, stannous octoate, zinc acetate, butyl titanate, appointing in p-methyl benzenesulfonic acid
Meaning is one or more of, and the dosage of catalyst is the moles total number or aliphatic dibasic acid of aliphatic dibasic acid and oxydibenzoic acid
With the 0.5%-1.0% of the moles total number of oxydibenzoic acid dimethyl ester.
8. thermoplastic aliphatic as described in claim 1-aromatic copolyester ester elastomer can give birth to preparing macromolecular thermoplastic
Application in terms of object degradation elastomeric article.
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Cited By (2)
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| CN112062939A (en) * | 2020-09-15 | 2020-12-11 | 常州大学 | High-resilience polylactic acid block copolymer and preparation method thereof |
| CN112898550A (en) * | 2021-01-27 | 2021-06-04 | 唐山睿安科技有限公司 | Biodegradable polyester and preparation method thereof |
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| CN112898550A (en) * | 2021-01-27 | 2021-06-04 | 唐山睿安科技有限公司 | Biodegradable polyester and preparation method thereof |
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| Publication number | Publication date |
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| CN109320699B (en) | 2020-11-24 |
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