CN107573491A - Adjustable polyester polymer of a kind of capable of being fast degraded and glass transition temperature and preparation method thereof - Google Patents
Adjustable polyester polymer of a kind of capable of being fast degraded and glass transition temperature and preparation method thereof Download PDFInfo
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- CN107573491A CN107573491A CN201610519873.2A CN201610519873A CN107573491A CN 107573491 A CN107573491 A CN 107573491A CN 201610519873 A CN201610519873 A CN 201610519873A CN 107573491 A CN107573491 A CN 107573491A
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Abstract
The invention discloses adjustable polyester polymer of a kind of capable of being fast degraded and glass transition temperature and preparation method thereof, described polyester polymer has following general structure：Wherein：A is rigid molecular structure unit, has following chemical structure of general formula：B is flexible molecule structure unit, has following chemical structure of general formula：C is degradable molecular structure unit, has following chemical structure of general formula：
Description
Technical field
The present invention relates to a kind of polyester polymer and preparation method thereof, specifically, be related to it is a kind of capable of being fast degraded and
Adjustable polyester polymer of glass transition temperature and preparation method thereof, belongs to Functional polymer materials technology field.
Background technology
Polyester is the polymer general name as obtained by polyalcohol and polyacid polycondensation, with PET (PET)
Changed for the aromatic polyester of representative with its excellent chemical stability, preferable mechanics and sanitation performance and transparent performance etc.
The industries such as fine, packaging are widely applied.At present, polyester output and sales volume still keep strong growth, especially
It is in terms of the packaging of soda；With the breakthrough that polyester barrier property is studied, in fields such as beer, food and cosmetics
Application the market for making polyester is further expanded.
But PET Polyester wastes are difficult natural degradation in nature.Polyester bottles are 45%~100% in humidity, temperature
To exist 30~40 years in 20 DEG C of environment, its performance only has 50% loss；Under the same terms, mylar may have 90
~100 years as long as.Immense pressure will be brought for this substantial amounts of Polyester waste to environment.If PET kind polyesters can be effectively controlled to give up
Existence time of the gurry in nature, its pollution to environment is avoided, will be birdsed of the same feather flock together the environmental-protecting performance of ester material to improving PET,
So as to promote its long term growth highly beneficial.
And the chemical factor for influenceing material degradation performance is many, such as：High molecular hydrophily is strong, easily hydrolysis；Molecule
Chain is soft, glass transition temperature is low is advantageous to degrade；Degradability also strengthens with the reduction of molecular mass；The group of high polymer
Into such as blending, copolymerization can also influence its degradation property.
Because PET is hemicrystalline high polymer, its starting stage degraded occurs to determine in the relatively loose nothing of structure
Type area and the edge of crystal region, and after the hydrolysis of connection molecule chain, generation chain cracking between crystal fine grain, it can cause unformed
Area further crystallizes, and crystallinity is substantially increased, so as to hinder the further generation of hydrolysis；On the other hand, molecule chain rigidity
Improve, the mobility of macromolecular necessarily reduces, shows that glass transition temperature is higher, thus can also make polymer to the quick of hydrolysis
Perception weakens.Therefore, just need to reduce the crystal property and glass transition temperature of polymer to improve the degradability of PET polyester,
Its weak ester bond is attacked because the reduction of crystallinity can make hydrone or microorganism effectively invade the inside of material, and
The reduction of glass transition temperature can improve the mobility of strand and reduce the energy required for change state, and then improve poly-
Sensitiveness of the ester to hydrolysis.
Because glass transition is the phenomenon relevant with molecular motion, and molecular motion and molecular structure have close pass
System, so that the factor for influenceing polymer glass temperature is numerous and extremely complex, influence factor includes chain flexibility, branched feelings
Condition, the regularity of chain, molecular weight, intermolecular force, the chain link ratio of heterogeneity and each group are into weight fraction of chain link etc.；
Further, since the Tg values of polymer can directly influence the performance and processing characteristics of the polymeric material；Therefore, how to lead to
Cross that structure design is realized while polyester polymer is capable of being fast degraded and glass transition temperature can adjust, will be to promoting polyester birds of the same feather flock together
The extensive use and long term growth of compound have far reaching significance.
The content of the invention
In view of the above-mentioned problems existing in the prior art and demand, it is an object of the invention to provide a kind of capable of being fast degraded and glass
Adjustable polyester polymer of glass temperature and preparation method thereof, to promote the extensive use of polyester polymer and long-range hair
Exhibition.
For achieving the above object, the technical solution adopted by the present invention is as follows：
A kind of adjustable polyester polymer of capable of being fast degraded and glass transition temperature, has following general structure：
Wherein：
A is rigid molecular structure unit, has following chemical structure of general formula：
B is flexible molecule structure unit, has following chemical structure of general formula：
C is degradable molecular structure unit, has following chemical structure of general formula：
R1、R2、R3、R4、R5、R6、R7、R8It is respectively and independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted miscellaneous
Alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted Heterocyclylalkyl, substituted or unsubstituted aryl, substitution or not
Any one in substituted heteroaryl, substituted or unsubstituted alkoxy, ester group, nitro, amino, amide groups, mercapto；
N is greater than 1 natural number；
Q is 1 to 5 natural number；
R, s, v are greater than the 0, natural number less than 11；
AndNatural number,
Preferably, n is the natural number more than 2.
Preferably, q is 1 to 3 natural number.
Preferably,Natural number.
Preferably,
Preferably, the A has following chemical structure of general formula：
Wherein：R1、R2、R3It is respectively and independently selected from H or unsubstituted alkyl (such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl
Base, tert-butyl group etc.), r is 2 to 6 natural number.
As further preferred scheme, the A has following chemical structure of general formula：
Wherein：R is 2 or 4.
Preferably, the B has following chemical structure of general formula：
Wherein：R2、R3、R4、R5It is respectively and independently selected from H or unsubstituted
Alkyl (such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group), s are 2 to 4 natural number, and r is 2 to 6
Natural number.
As further preferred scheme, the B has following chemical structure of general formula：
Wherein：S and r each stands alone as 2 or 4.
Preferably, the C has following chemical structure of general formula：
Wherein：R6、
R7、R8It is respectively and independently selected from H or unsubstituted alkyl (such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group
Deng), v is 1 to 4 natural number.
As further preferred scheme, the C has following chemical structure of general formula：
Wherein：R is H or methyl.
The preparation method of the adjustable polyester polymer of of the present invention capable of being fast degraded and glass transition temperature, including
Following steps：
A) willAntimony system is catalyzed
Agent and stabilizer are added in pressure vessel, under an inert atmosphere, at 0.1~0.5mPa and 200~260 DEG C stirring reaction to ester
Change dehydration rate and reach the 95% of theoretical value；
B) 160~200 DEG C are cooled to, adds C segments：
First vacuumize
It is 20000~30000Pa to reactor pressure, then maintains vacuum, carries out insulated and stirred and react 1~3 hour；Take out again true
Sky to reactor pressure is below 100Pa, and is slowly heated to 260~290 DEG C, then maintains vacuum, carries out insulation and stir
Mix reaction 1~4 hour；
C) room temperature is cooled to, collects solid, produces described polyester polymer.
R therein1、R2、R3、R4、R5、R6、R7、R8And r, s, v, q definition are same as above.
Preferably, the preparation of the C segments comprises the following steps：
1. willIt is dissolved in organic solvent with acid binding agent, then addsX therein is halogen element (being preferably chlorine or bromine), and R ' is alkyl (being preferably methyl or ethyl)；
2. drop finishes, it is stirred at room temperature to there is white precipitate；
3. adding organic solvent, continue to be stirred at room temperature at least 12 hours；
4. filtering, filtrate is washed with water in neutrality, then dry, filtering and concentration, gained solid is C segments.
Preferably, the antimony-based catalyst selects antimony oxide (Sb2O3), antimony acetate (Sb
(CH3COO)3), antimony glycol [Sb2(OCH2CH2CO)3At least one of].
Preferably, the stabilizer is selected in phosphoric acid, phosphorous acid, trimethyl phosphate, triphenyl phosphate at least
It is a kind of.
Preferably, R therein1、R2、R3、R4、R5、R6、R7、R8It is independently chosen from H or unsubstituted alkyl (such as first
Base, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, tert-butyl group etc.), s be 2 to 4 natural number, v be 1 to 4 natural number, r
For 2 to 6 natural number.
Compared with prior art, the present invention has the advantages that：
It our experiments show that：Polyester polymer provided by the invention not only has fast degradation under given conditions special
Property, and controllability of the glass transition temperature in the range of -30~65 DEG C can be realized, and there is good machining property
Can, the extensive use that such polymer can be achieved requires, can especially ensure the feature of environmental protection of such polymer；In addition, the present invention
Preparation method is simple, and cost is low, and raw material is cheap and easy to get, is easy to large-scale production, has conspicuousness progress relative to prior art
With far-reaching social effect.
Brief description of the drawings
Fig. 1 is the DSC curve of the polyester polymer prepared by embodiment l, and the A curves in figure are bent to heat for the first time
Line, B curves are first time cooling curve, and C curve is second of heating curves；
Fig. 2 is the degradation property curve of the polyester polymer prepared by embodiment l.
Embodiment
Technical scheme is made further in detail, intactly to illustrate with reference to embodiment and accompanying drawing.Following realities
Experimental method described in example is applied, is conventional method unless otherwise specified；The reagent and material, unless otherwise specified,
Obtain from commercial channels.
Chemical analysis method and analytical instrument employed in the present invention are described as follows：
First, inherent viscosity (IV) determines
The PET standard assays of industrial quarters：It is poly- according to obtained by association of plastics industry (SPI ' s) on PET canonical measure
Compound is in phenol/1,1,2,2- tetrachloroethanes (60:40 weight ratios) in mixed solution, with determination of ubbelohde viscometer, measurement temperature
For 25 DEG C.
Because the PET degree of polymerization is calculated by below equation：DPn=1.19 × IV -7；Wherein, IV unit is milli
/ gram (mL/g) is risen, therefore the chain length of the polyester in the present invention is estimated using identical computational methods.
2nd, chemical composition and structure
The structure for the polyester polymer that the present invention is prepared is determined with composition by solution nuclear magnetic resonance, nuclear magnetic resonance
Measurement temperature be 20 degree Celsius, solvent is deuterochloroform.
3rd, thermal performance test
The hot property for the polyester polymer that the present invention is prepared is the differential scanning calorimeter in PerkinElmer
Measure obtains in DSC4000.
4th, degradation property is tested
It is small that the test polyester polymer that is prepared of the present invention stirs n in 80 DEG C, 10% sodium hydrate aqueous solution
When after percent weight loss.
5th, Mechanics Performance Testing
Tensile strength test is determined by Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry according to ASTMD638-97 methods.
Embodiment 1
First, segment C is prepared
33.23g terephthalic acid (TPA)s and 84mL triethylamines are dissolved in 50mL dichloromethane；To above-mentioned mixed solution and dripping
65.11g chloracetic acid methyl esters；Drop finishes, and stirs at room temperature to when there are white precipitate (about 5 hours), adds 100mL dichloromethanes
Alkane, continue stirring 24 hours at room temperature；Filtering, ammonia remaining in filtrate is washed with water in neutrality；Done with anhydrous magnesium sulfate
It is dry, filtering, filtrate is concentrated, obtains 55.80g solids, as described segment C, molar yield 90%.
1HNMR(CDCl3,400Mz)δ8.18(D,4H)；δ4.89(S,4H)；δ3.81(S,6H).
2nd, polyester polymer of the present invention is prepared
199.2g terephthalic acid (TPA)s, 94.4g succinic acid, 210.8g ethylene glycol, 0.2g antimony glycols, 0.1g phosphoric acid are added
It is 0.2mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating stirring is simultaneously in Stainless steel pressure vessels
230 DEG C of reactions are maintained, while by being fractionated water caused by elimination reaction, react the water generated by weighing to judge to react
Degree.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, the above-mentioned segment C of 40.3g is added, first takes out
Vacuum to reactor pressure is 20000Pa, then maintains vacuum, carries out insulated and stirred and reacts 1 hour；Gradually vacuumize again
Below 100Pa is down to reactor pressure, and is slowly heated to 260~290 DEG C, then maintains vacuum, insulation is carried out and stirs
Mix reaction 3 hours；Room temperature is cooled to, solid is collected, produces polyester polymer of the present invention.
According to association of plastics industry (SPI ' s) on PET canonical measure resulting polymers in phenol/1,1,2,2- tetrachloros
Ethane (60:40 weight ratios) viscosity in mixed solution is 0.809dL/g.
In addition, the chain length for learning the polyester polymer that the present embodiment is obtained is calculated according to B.Gantillon formula
It is equivalent to the degree of polymerization：
DPn=1.19 × IV -7=1.19 × (0.809 × 100) -7=89
Conventional PET chain length.
Fig. 1 is that the DSC curve figure that thermal performance test (10 DEG C/min of programming rate) obtains is carried out to obtained polymer,
As seen from Figure 1：The glass transition temperature of resulting polymers is 31.21 DEG C, nodeless mesh temperature and melting temperature, is showed without fixed
Kenel；The melting temperature and glass transition temperature for illustrating polyester polymer provided by the invention are sent out compared to conventional PET
Obvious change is given birth to.
Fig. 2 embodies polyester polymer prepared by the present embodiment and stirred in 80 DEG C, 10% sodium hydrate aqueous solution
The reduced gravity situations after n hours are mixed, as seen from Figure 2：Polyester polymer prepared by the present embodiment stirs 120 points in aqueous slkali
Zhong Hou, percent weight loss reach 64.6%；After stirring 240 minutes, percent weight loss reaches 91.6%；In stirring 420 minutes
Afterwards, percent weight loss reaches 100%；Illustrate that polyester polymer provided by the present invention has fast degradation under given conditions
Characteristic.
In addition, the elasticity for the polyester polymer that the present embodiment is obtained is measured according to ASTMD638-97 testing standard
Modulus is 592.29MPa, tensile stress 30.2MPa.
Embodiment 2
First, segment C is prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
By 166.1g terephthalic acid (TPA)s, 118.1g succinic acid, 210.8g ethylene glycol, 0.1g antimony glycols, 0.1g phosphorous acid
Add in Stainless steel pressure vessels, be 0.2mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating is stirred
Mix and maintain 240 DEG C of reactions, while by being fractionated water caused by elimination reaction, react the water generated by weighing to judge
The extent of reaction.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, adds the above-mentioned segment C of 40.3g,
It is 20000Pa to be first evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 1.5 hours；It is gradual again
It is evacuated to reactor pressure and is down to below 100Pa, and be slowly heated to 260~290 DEG C, then maintain vacuum, carries out
Insulated and stirred is reacted 3 hours；Room temperature is cooled to, solid is collected, produces polyester polymer of the present invention.
After tested：The inherent viscosity IV=0.863 of resulting polymers, degree of polymerization DPn=96；Glass transition temperature is
22.28 DEG C, nodeless mesh temperature and melting temperature show unformed shape；Modulus of elasticity is 615.25MPa, and tensile stress is
56.32MPa；Percent weight loss after being stirred 360 minutes in 80 DEG C, 10% sodium hydrate aqueous solution is 100%.
Embodiment 3
First, segment C is prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
747g terephthalic acid (TPA)s, 59g succinic acid, 527g ethylene glycol, 2g antimony oxides, 0.8g trimethyl phosphates are added
It is 0.25mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating stirring is simultaneously in Stainless steel pressure vessels
245 DEG C of reactions are maintained, while by being fractionated water caused by elimination reaction, react the water generated by weighing to judge to react
Degree.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, the above-mentioned segment C of 100.8g is added, first takes out
Vacuum to reactor pressure is 20000Pa, then maintains vacuum, carries out insulated and stirred and reacts 1.5 hours；Gradually take out again true
Sky to reactor pressure is down to below 100Pa, and is slowly heated to 260~290 DEG C, then maintains vacuum, is incubated
Stirring reaction 1.5 hours；Room temperature is cooled to, solid is collected, produces polyester polymer of the present invention.
After tested：The inherent viscosity IV=0.637 of resulting polymers, degree of polymerization DPn=69；Glass transition temperature is
55.82 DEG C, melting temperature is 202.28 DEG C；Modulus of elasticity is 602.04MPa, tensile stress 39.07MPa；80 DEG C, 10%
Sodium hydrate aqueous solution in stir 480 minutes after percent weight loss be 92.35%.
Embodiment 4
First, segment C is prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
By 2124.8g terephthalic acid (TPA)s, 377.6g succinic acid, 1587.2g ethylene glycol, 3.2g antimony glycols, 1.8g phosphoric acid
Triphenylmethyl methacrylate is added in Stainless steel pressure vessels, is 0.3mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor,
Heating stirring simultaneously maintains 220 DEG C of reactions, while by being fractionated water caused by elimination reaction, the water of generation is reacted by weighing
To judge the extent of reaction.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, by the above-mentioned chains of 330.7g
Section C is added in reactor, and it is 30000Pa to be evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred reaction
1.5 hour；Reactor pressure is evacuated to again and is down to below 100Pa, and is slowly heated to 260~290 DEG C, then remains true
Reciprocal of duty cycle, carry out insulated and stirred and react 2.5 hours；Room temperature is cooled to, the solid for collecting to obtain is polyesters of the present invention
Polymer.
After tested：The inherent viscosity IV=0.648 of resulting polymers, degree of polymerization DPn=70, glass transition temperature is
47.56 DEG C, melting temperature is 190.21 DEG C, modulus of elasticity 698.98MPa, tensile stress 48.52MPa；80 DEG C, 10%
Sodium hydrate aqueous solution in stir 450 minutes after percent weight loss be 100%.
Embodiment 5
First, segment C is prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
By 199.4g terephthalic acid (TPA)s, 116.8g adipic acids, 210.8g ethylene glycol, 0.15g antimony oxides, 0.1g phosphorus
Acid, add in Stainless steel pressure vessels, be 0.2mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating
Stir and maintain 240 DEG C of reactions, while by being fractionated water caused by elimination reaction, react the water generated by weighing to sentence
The disconnected extent of reaction.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, adds the above-mentioned segments of 40.3g
C, it is 20000Pa to be first evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 1 hour；It is gradual again
It is evacuated to reactor pressure and is down to below 100Pa, and be slowly heated to 260~290 DEG C, then maintain vacuum, carries out
Insulated and stirred is reacted 1.5 hours；Room temperature is cooled to, solid is collected, produces polyester polymer of the present invention.
After tested：The inherent viscosity IV=0.841 of resulting polymers, degree of polymerization DPn=93；Glass transition temperature is
14.75 DEG C, nodeless mesh temperature and melting temperature show unformed shape；Modulus of elasticity is 57MPa, and tensile stress is
20.68MPa；Percent weight loss after being stirred 430 minutes in 80 DEG C, 10% sodium hydrate aqueous solution is 100%.
Embodiment 6
First, segment C is prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
By 298.8g terephthalic acid (TPA)s, 29.2g adipic acids, 161.2g ethylene glycol, 0.1g antimony oxides, 0.06g phosphoric acid
Add in Stainless steel pressure vessels, be 0.35mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating is stirred
Mix and maintain 245 DEG C of reactions, while by being fractionated water caused by elimination reaction, react the water generated by weighing to judge
The extent of reaction.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, adds the above-mentioned segment C of 40.3g,
It is 20000Pa to be evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 1 hour；Gradually take out again true
Sky to reactor pressure is down to below 100Pa, and is slowly heated to 260~290 DEG C, then maintains vacuum, is incubated
Stirring reaction 2 hours；Room temperature is cooled to, solid is collected, produces polyester polymer of the present invention.
After tested：The inherent viscosity IV=0.667 of resulting polymers, degree of polymerization DPn=72, glass transition temperature is
64.97 DEG C, melting temperature is 204.35 DEG C；Modulus of elasticity is 392.92MPa, tensile stress 47.97MPa；80 DEG C, 10%
Sodium hydrate aqueous solution in stir 480 minutes after percent weight loss be 77.6%.
Embodiment 7
First, segment C is prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
By 929.6g terephthalic acid (TPA)s, 350.4g adipic acids, 1224g1,4- butanediols, 2.4g antimony oxides, 1.0g phosphorus
Triphenyl phosphate ester is added in Stainless steel pressure vessels, is with pressure in maintenance reaction device after air in nitrogen displacement reactor
0.1mPa, heating stirring simultaneously maintain 205 DEG C of reactions, while by being fractionated water caused by elimination reaction, by weighing reaction life
Into water judge the extent of reaction.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, added
The above-mentioned segment C of 165.3g, it is 20000Pa to be first evacuated to reactor pressure, then maintains vacuum, and it is anti-to carry out insulated and stirred
Answer 2 hours；Reactor pressure is gradually evacuated to again and is down to below 100Pa, and is slowly heated to 260~290 DEG C, Ran Houwei
Vacuum is held, insulated and stirred is carried out and reacts 2 hours；Room temperature is cooled to, solid is collected, produces polyester Type of Collective of the present invention
Thing.
After tested：The inherent viscosity IV=0.777 of resulting polymers, degree of polymerization DPn=85, glass transition temperature is
0.3 DEG C, melting temperature is 164.4 DEG C.
Embodiment 8
First, segment C is prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
By 796.8g terephthalic acid (TPA)s, 467.2g adipic acids, 168.6g ethylene glycol, 979.2g1,4- butanediols, 1.6g tri-
Aoxidize in two antimony, 0.6g triphenyl phosphates addition Stainless steel pressure vessels, with maintenance reaction after air in nitrogen displacement reactor
Pressure is 0.3mPa in device, and heating stirring simultaneously maintains 235 DEG C of reactions, while by being fractionated water caused by elimination reaction, passes through
The water for weighing reaction generation judges the extent of reaction.When esterification yield reaches 95%, reactor temperature is down to 160~
200 DEG C, the above-mentioned segment C of 165.3g are added, it is 20000Pa to be first evacuated to reactor pressure, then maintains vacuum, is carried out
Insulated and stirred is reacted 1 hour；Reactor pressure is gradually evacuated to again is down to below 100Pa, and it is slowly heated to 260~
290 DEG C, vacuum is then maintained, insulated and stirred is carried out and reacts 2.5 hours；Room temperature is cooled to, solid is collected, produces institute of the present invention
The polyester polymer stated.
After tested：The inherent viscosity IV=0.737 of resulting polymers, degree of polymerization DPn=81, glass transition temperature for-
7.83 DEG C, melting temperature is 128.45 DEG C.
Embodiment 9
First, segment C is prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
By 1328g terephthalic acid (TPA)s, 1752g adipic acids, 2880g 1,4- butanediols, 6.16g antimony oxides, 2.8g phosphorus
Triphenyl phosphate ester is added in Stainless steel pressure vessels, is with pressure in maintenance reaction device after air in nitrogen displacement reactor
0.15mPa, heating stirring simultaneously maintain 215 DEG C of reactions, while by being fractionated water caused by elimination reaction, by weighing reaction life
Into water judge the extent of reaction.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, added
The above-mentioned segment C of 413.3g, it is 20000Pa to be first evacuated to reactor pressure, then maintains vacuum, and it is anti-to carry out insulated and stirred
Answer 2 hours；Reactor pressure is gradually evacuated to again and is down to below 100Pa, and is slowly heated to 260~290 DEG C, Ran Houwei
Vacuum is held, insulated and stirred is carried out and reacts 2.5 hours；Room temperature is cooled to, solid is collected, produces polyester of the present invention and birds of the same feather flock together
Compound.
After tested：The inherent viscosity IV=0.89 of resulting polymers, degree of polymerization DPn=99, glass transition temperature for-
29.82 DEG C, melting temperature is 101.68 DEG C.
Finally be necessary described herein be：Above example is served only for further detailed to technical scheme work
Ground explanation, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to the above of the invention
Some the nonessential modifications and adaptations made belong to protection scope of the present invention.
Claims (10)
1. the adjustable polyester polymer of a kind of capable of being fast degraded and glass transition temperature, it is characterised in that there is following structure
Formula：Wherein：
A is rigid molecular structure unit, has following chemical structure of general formula：
B is flexible molecule structure unit, has following chemical structure of general formula：
C is degradable molecular structure unit, has following chemical structure of general formula：
R1、R2、R3、R4、R5、R6、R7、R8It is respectively and independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted miscellaneous alkane
Base, substituted or unsubstituted cycloalkyl, substituted or unsubstituted Heterocyclylalkyl, substituted or unsubstituted aryl, substitution do not take
Any one in the heteroaryl in generation, substituted or unsubstituted alkoxy, ester group, nitro, amino, amide groups, mercapto；
N is greater than 1 natural number；
Q is 1 to 5 natural number；
R, s, v are greater than the 0, natural number less than 11；
AndNatural number,
2. polyester polymer according to claim 1, it is characterised in that the A has following chemical structure of general formula：
Wherein：R1、R2、R3It is respectively and independently selected from H or unsubstituted alkyl, r
For 2 to 6 natural number.
3. polyester polymer according to claim 1, it is characterised in that the B has following chemical structure of general formula：
Wherein：R2、R3、R4、R5It is respectively and independently selected from H or unsubstituted alkane
Base, s are 2 to 4 natural number, and r is 2 to 6 natural number.
4. polyester polymer according to claim 1, it is characterised in that the C has following chemical structure of general formula：
Wherein：R6、R7、R8
H or unsubstituted alkyl is respectively and independently selected from, v is 1 to 4 natural number.
A kind of 5. method for preparing the polyester polymer described in claim 1, it is characterised in that comprise the following steps：
A) willAntimony-based catalyst and
Stabilizer is added in pressure vessel, and stirring reaction is de- to being esterified under an inert atmosphere, at 0.1~0.5mPa and 200~260 DEG C
Water rate reaches the 95% of theoretical value；
B) 160~200 DEG C are cooled to, adds C segments：
First it is evacuated to anti-
It is 20000~30000Pa to answer pressure in device, then maintains vacuum, carries out insulated and stirred and reacts 1~3 hour；It is evacuated to again
Reactor pressure is below 100Pa, and is slowly heated to 260~290 DEG C, then maintains vacuum, and it is anti-to carry out insulated and stirred
Answer 1~4 hour；
C) room temperature is cooled to, collects solid, produces described polyester polymer；
R therein1、R2、R3、R4、R5、R6、R7、R8And r, s, v, q definition are the same as described in claim 1.
6. according to the method for claim 5, it is characterised in that the preparation of the C segments comprises the following steps：
1. willIt is dissolved in organic solvent with acid binding agent, then addsX therein is halogen element, and R ' is alkyl；
2. drop finishes, it is stirred at room temperature to there is white precipitate；
3. adding organic solvent, continue to be stirred at room temperature at least 12 hours；
4. filtering, filtrate is washed with water in neutrality, then dry, filtering and concentration, gained solid is C segments.
7. according to the method for claim 6, it is characterised in that：Described X is chlorine or bromine, and described R ' is methyl or second
Base.
8. according to the method for claim 5, it is characterised in that：The antimony-based catalyst is selected from antimony oxide, vinegar
At least one of sour antimony, antimony glycol.
9. according to the method for claim 5, it is characterised in that：The stabilizer is from phosphoric acid, phosphorous acid, tripotassium phosphate
At least one of ester, triphenyl phosphate.
10. according to the method for claim 5, it is characterised in that：R therein1、R2、R3、R4、R5、R6、R7、R8Independent choosing
From H or unsubstituted alkyl, s is 2 to 4 natural number, and v is 1 to 4 natural number, and r is 2 to 6 natural number.
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| CN115667361A (en) * | 2020-03-11 | 2023-01-31 | 埃德温·W·黄 | Autocatalytic rapid degradation polyester polymer and preparation method and application thereof |
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| CN115667361A (en) * | 2020-03-11 | 2023-01-31 | 埃德温·W·黄 | Autocatalytic rapid degradation polyester polymer and preparation method and application thereof |
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