CN107573492A - Adjustable and capable of being fast degraded polyester polymer of a kind of glass transition temperature and preparation method thereof - Google Patents
Adjustable and capable of being fast degraded polyester polymer of a kind of glass transition temperature and preparation method thereof Download PDFInfo
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Abstract
The invention discloses adjustable and capable of being fast degraded polyester polymer of a kind of 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 a kind of glass transition temperature can
Regulation and polyester polymer capable of being fast degraded and preparation method thereof, belong 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.Therefore, substantial amounts of Polyester waste will bring immense pressure 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 glass transition temperature is adjustable
Section and polyester polymer capable of being fast degraded 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 glass transition temperature can adjust and polyester polymer capable of being fast degraded, 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、R8、R9It is respectively and independently selected from H, substituted or unsubstituted alkyl, substitution or unsubstituted
Miscellaneous alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted Heterocyclylalkyl, substituted or unsubstituted aryl, substitution
It is or any one in unsubstituted heteroaryl, substituted or unsubstituted alkoxy, ester group, nitro, amino, amide groups, mercapto
Kind;
N is greater than 1 natural number;
Q is 1 to 5 natural number;
R, s, u, 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、R8、R9Respectively
It is independently selected from H or unsubstituted alkyl (such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group), u 2
To 4 natural number, 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, and u is 2 or 4.
The preparation method of the adjustable and capable of being fast degraded polyester polymer of glass transition temperature of the present invention, 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 220~260 DEG C stirring reaction to ester
Change dehydration rate and reach the 95% of theoretical value;
B) 160~220 DEG C are cooled to, adds C segments:First
It is 20000~30000Pa to be evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 1~3 hour;
It is below 100Pa to be evacuated to reactor pressure again, and is slowly heated to 240~280 DEG C, then maintains vacuum, is carried out
Insulated and stirred is reacted 1~4 hour;
C) room temperature is cooled to, collects solid, produces described polyester polymer;
R therein1、R2、R3、R4、R5、R6、R7、R8、R9And r, s, u, 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 adds
X 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、R8、R9It is independently chosen from H or unsubstituted alkyl
(such as methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group), u and s are 2 to 4 natural number, and v is 1 to 4
Natural number, r be 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 5~65 DEG C can be realized, and there is good machining property,
The extensive use that such polymer can be achieved requires, can especially ensure the feature of environmental protection of such polymer;In addition, the preparation of the present invention
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 and depth relative to prior art
Remote 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;
Fig. 3 is the DSC curve of the polyester polymer prepared by embodiment 5, 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. 4 is the degradation property curve of the polyester polymer prepared by embodiment 5.
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, C segments are prepared
23.62g succinic acid 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 47.20g solids, as described C segments, molar yield 90%.
1HNMR(CDCl3,400Mz)δ4.66(S,4H);δ3.77(S,6H);δ2.80(T,4H).
2nd, polyester polymer of the present invention is prepared
298.8g terephthalic acid (TPA)s, 29.2g adipic acids, 210.8g ethylene glycol, 0.2g antimony oxides, 0.1g phosphoric acid are added
Enter in Stainless steel pressure vessels, be 0.3mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating stirring
And 230 DEG C of reactions are maintained, while by being fractionated water caused by elimination reaction, the water that generation is reacted by weighing is anti-to judge
Answer degree.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, adds the above-mentioned C segments of 34.7g, first
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 260~280 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.
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 0.671dL/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 × 100) -7=1.19 × (0.671 × 100) -7=73
Conventional PET chain length.
Fig. 1 is that the DSC curve that thermal performance test (heating rate is 10 DEG C/min) obtains is carried out to obtained polymer
Figure, as seen from Figure 1:The glass transition temperature of resulting polymers is 47.62 DEG C, and melting temperature is 199.16 DEG C, temperature-rise period
Middle recrystallization temperature is 126.97 DEG C;Illustrate the melting temperature and glass transition temperature of polyester polymer provided by the invention
Change compared to conventional PET there occurs obvious.
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 26.45%;After stirring 240 minutes, percent weight loss reaches 46.05%;In 480 points of stirring
Zhong Hou, percent weight loss reach 79.2%;It is quick to illustrate that polyester polymer provided by the present invention has under given conditions
Degradation 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 656.2MPa, tensile stress 47.09MPa.
Embodiment 2
First, C segments are prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
By 199.2g terephthalic acid (TPA)s, 116.8g adipic acids, 210.8g ethylene glycol, 0.2g antimony oxides, 0.08g phosphoric acid
Trimethyl is added in Stainless steel pressure vessels, is 0.4mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor,
Heating stirring simultaneously maintains 242 DEG C of reactions, while by being fractionated water caused by elimination reaction.By the water for weighing reaction generation
To judge the extent of reaction.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, adds the above-mentioned C of 34.7g
Segment, it is 25000Pa to be first evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 1 hour;Again
Gradually being evacuated to reactor pressure is down to below 100Pa, and is slowly heated to 260~280 DEG C, then maintains vacuum,
Insulated and stirred is carried out to react 1.5 hours;Room temperature is cooled to, solid is collected, produces polyester polymer of the present invention.
After tested:The inherent viscosity IV=0.816 of resulting polymers, degree of polymerization DPn=90;Glass transition temperature is
11.24 DEG C, melting temperature is 135.45 DEG C;Modulus of elasticity is 25.21MPa, tensile stress 17.96MPa;80 DEG C, 10%
Sodium hydrate aqueous solution in stir 450 minutes after percent weight loss be 100%.
Embodiment 3
First, C segments are prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
664g terephthalic acid (TPA)s, 146g adipic acids, 465g ethylene glycol, 1.25g antimony glycols, 0.5g triphenyl phosphates are added
Enter in Stainless steel pressure vessels, be 0.3mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating stirring
And 246 DEG C of reactions are maintained, while by being fractionated water caused by elimination reaction.Judged by weighing the water of reaction generation anti-
Answer degree.When esterification yield reaches 95%, reactor temperature is down to 200~220 DEG C, the above-mentioned C segments of 87.3g added anti-
Answer in device, it is 20000Pa to be first evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 2 hours;
It is below 100Pa to be evacuated to reactor pressure again, and is heated to 240~280 DEG C, then maintains vacuum, is incubated
Stirring reaction 3 hours;Room temperature is cooled to, the solid for collecting to obtain is polyester polymer of the present invention.
After tested:The inherent viscosity IV=0.762 of resulting polymers, degree of polymerization DPn=84;Glass transition temperature is
34.57 DEG C, melting temperature is 174.56 DEG C;Modulus of elasticity is 23MPa, tensile stress 40.68MPa;In 80 DEG C, 10% hydrogen
Percent weight loss after being stirred 480 minutes in aqueous solution of sodium oxide is 90.05%.
Embodiment 4
First, C segments are prepared
With embodiment 1.
2nd, polyester polymer of the present invention is prepared
By 1394.4g terephthalic acid (TPA)s, 525.6g adipic acids, 930g ethylene glycol, 3.5g antimony glycols, 1.5g phosphoric acid triphens
Ester is added in Stainless steel pressure vessels, is 0.3mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating
Stir and maintain 252 DEG C of reactions, while by being fractionated water caused by elimination reaction.Sentenced by weighing the water of reaction generation
The disconnected extent of reaction.When esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, by the above-mentioned C segments of 208.2g
Add in reactor, it is 20000Pa to be first evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred reaction 2
Hour;It is below 100Pa to be evacuated to reactor pressure again, and is heated to 260~280 DEG C, then maintains vacuum, is carried out
Insulated and stirred is reacted 3 hours;Room temperature is cooled to, the solid for collecting to obtain is polyester polymer of the present invention.
After tested:The inherent viscosity IV=0.829 of resulting polymers, degree of polymerization DPn=92, glass transition temperature is
17.78 DEG C, melting temperature is 158.21 DEG C;Modulus of elasticity is 97.9MPa, tensile stress 21.39MPa;80 DEG C, 10%
Percent weight loss after being stirred 420 minutes in sodium hydrate aqueous solution is 100%.
Embodiment 5
First, C segments are prepared
29.23g adipic acids 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 52.20g solids, as described C segments, molar yield 90%.
1HNMR(CDCl3,400Mz)δ4.62(S,4H);δ3.77(S,6H);δ2.47(T,4H);δ1.75(M,4H).
2nd, polyester polymer of the present invention is prepared
By 298.8g terephthalic acid (TPA)s, 23.6g succinic acid, 210.8g ethylene glycol, 0.2g antimony glycols, 0.08g tricresyl phosphates
Phenyl ester is added in Stainless steel pressure vessels, is 0.2mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, is added
Thermal agitation simultaneously maintains 220 DEG C of reactions, while by being fractionated water caused by elimination reaction.By weigh reaction generation water come
Judge the extent of reaction, when esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, adds the above-mentioned C chains of 38.7g
Section, it is 20000Pa to be first evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 1 hour;Again by
Gradually it is evacuated to reactor pressure and is down to below 100Pa, and be slowly heated to 260~280 DEG C, then maintains vacuum, enter
Row insulated and stirred is reacted 1 hour;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 0.676dL/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 × (0.676 × 100) -7=73
Conventional PET chain length.
Fig. 3 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 3:The glass transition temperature of resulting polymers is 51.22 DEG C, and melting temperature is 204.23 DEG C, weight in temperature-rise period
Crystallization temperature is 134.24 DEG C;Illustrate that the melting temperature of polyester polymer provided by the invention is compared with glass transition temperature
Change in conventional PET there occurs obvious.
Fig. 4 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 4:Polyester polymer prepared by the present embodiment stirs 120 points in aqueous slkali
Zhong Hou, percent weight loss reach 40.5%;After stirring 240 minutes, percent weight loss reaches 57.1%;In stirring 480 minutes
Afterwards, percent weight loss reaches 70.6%;Illustrate that polyester polymer provided by the present invention has fast prompt drop under given conditions
Solve 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 740.68MPa, tensile stress 53.77MPa.
Embodiment 6
First, C segments are prepared
With embodiment 5.
2nd, polyester polymer of the present invention is prepared
By 298.8g terephthalic acid (TPA)s, 29.2g adipic acids, 210.8g ethylene glycol, 0.25g antimony oxides, 0.12g phosphoric acid
Triphenylmethyl methacrylate is added in Stainless steel pressure vessels, is 0.2mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor,
Heating stirring simultaneously maintains 245 DEG C of reactions, while by being fractionated water caused by elimination reaction.By the water for weighing reaction generation
To judge the extent of reaction, when esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, adds the above-mentioned C chains of 145g
Section, it is 20000Pa to be first evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 1 hour;Again by
Gradually it is evacuated to reactor pressure and is down to below 100Pa, and be slowly heated to 260~280 DEG C, then maintains vacuum, enter
Row insulated and stirred is reacted 3.5 hours;Room temperature is cooled to, solid is collected, produces polyester polymer of the present invention.
After tested:The inherent viscosity IV=0.634 of resulting polymers, degree of polymerization DPn=68;Glass transition temperature is
29.29℃;Percent weight loss after being stirred 250 minutes in 80 DEG C, 10% sodium hydrate aqueous solution is 100%.
Embodiment 7
First, C segments are prepared
With embodiment 5.
2nd, polyester polymer of the present invention is prepared
265.6g terephthalic acid (TPA)s, 47.2g succinic acid, 210.8g ethylene glycol, 0.5g antimony oxides, 0.2g phosphoric acid are added
Enter in Stainless steel pressure vessels, be 0.2mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating stirring
And 235 DEG C of reactions are maintained, while by being fractionated water caused by elimination reaction.Judged by weighing the water of reaction generation anti-
Degree is answered, when esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, the above-mentioned C segments of 38.7g 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 260~280 DEG C, then maintains vacuum, insulation is carried out and stirs
Mix reaction 2 hours;Room temperature is cooled to, solid is collected, produces polyester polymer of the present invention.
After tested:The inherent viscosity IV=0.713 of resulting polymers, degree of polymerization DPn=78;Glass transition temperature is
43.52 DEG C, melting temperature is 183.82 DEG C;Modulus of elasticity is 497MPa, tensile stress 31.53MPa;80 DEG C, 10%
Percent weight loss after being stirred 480 minutes in sodium hydrate aqueous solution is 88%.
Embodiment 8
First, C segments are prepared
With embodiment 5.
2nd, polyester polymer of the present invention is prepared
498g terephthalic acid (TPA)s, 236g succinic acid, 527g ethylene glycol, 1.6g antimony glycols, 0.75g triphenyl phosphates are added
Enter in Stainless steel pressure vessels, be 0.3mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating stirring
And 245 DEG C of reactions are maintained, while by being fractionated water caused by elimination reaction.Judged by weighing the water of reaction generation anti-
Degree is answered, when esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, the above-mentioned C segments of 96.8g are added into reaction
In device, it is 30000Pa to be first evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 1.5 hours;
It is below 100Pa to be evacuated to reactor pressure again, and is heated to 260~280 DEG C, then maintains vacuum, is incubated
Stirring reaction 3.5 hours;Room temperature is cooled to, the solid for collecting to obtain is polyester polymer of the present invention.
After tested:The inherent viscosity IV=0.823 of resulting polymers, degree of polymerization DPn=91, glass transition temperature is
24.26 DEG C, modulus of elasticity 37.72MPa, tensile stress 20.64MPa;Stirred in 80 DEG C, 10% sodium hydrate aqueous solution
The percent weight loss after 440 minutes is mixed as 100%.
Embodiment 9
First, C segments are prepared
With embodiment 5.
2nd, polyester polymer of the present invention is prepared
By 1743g terephthalic acid (TPA)s, 657g adipic acids, 1488g ethylene glycol, 5.6g antimony glycols, 2.8g trimethyl phosphates
Add in Stainless steel pressure vessels, be 0.25mPa with pressure in maintenance reaction device after air in nitrogen displacement reactor, heating is stirred
Mix and maintain 235 DEG C of reactions, while by being fractionated water caused by elimination reaction.Judged by weighing the water of reaction generation
The extent of reaction, when esterification yield reaches 95%, reactor temperature is down to 160~200 DEG C, the above-mentioned C segments of 1087.5g are added
In reactor, it is 25000Pa to be first evacuated to reactor pressure, then maintains vacuum, and it is small to carry out insulated and stirred reaction 1.5
When;It is below 100Pa to be evacuated to reactor pressure again, and is heated to 260~280 DEG C, then maintains vacuum, is protected
Warm stirring reaction 3.5 hours;Room temperature is cooled to, the solid for collecting to obtain is polyester polymer of the present invention.
After tested:The inherent viscosity IV=0.931 of resulting polymers, degree of polymerization DPn=104, glass transition temperature is
10.29 DEG C, the percent weight loss after being stirred 120 minutes in 80 DEG C, 10% sodium hydrate aqueous solution is 100%.
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. a kind of glass transition temperature can adjust and polyester polymer capable of being fast degraded, it is characterised in that described polyesters
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:
R1、R2、R3、R4、R5、R6、R7、R8、R9It 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, u, 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、R3H or unsubstituted alkyl is respectively and independently selected from, r is 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 alkyl, s
For 2 to 4 natural number, 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、R9Independently select
From H or unsubstituted alkyl, u is 2 to 4 natural number, and 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 steady
Determine agent add pressure vessel in, under an inert atmosphere, at 0.1~0.5mPa and 220~260 DEG C stirring reaction to be esterified dehydration
Rate reaches the 95% of theoretical value;
B) 160~220 DEG C are cooled to, adds C segments:First
It is 20000~30000Pa to be evacuated to reactor pressure, then maintains vacuum, carries out insulated and stirred and reacts 1~3 hour;
It is below 100Pa to be evacuated to reactor pressure again, and is slowly heated to 240~280 DEG C, then maintains vacuum, is carried out
Insulated and stirred is reacted 1~4 hour;
C) room temperature is cooled to, collects solid, produces described polyester polymer;
R therein1、R2、R3、R4、R5、R6、R7、R8、R9And r, s, u, 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 addsIts
In X be halogen element, 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 from antimony oxide, antimony acetate,
At least one of 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、R8、R9It is independent
Selected from H or unsubstituted alkyl, u and s are 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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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102516517A (en) * | 2011-12-13 | 2012-06-27 | 金发科技股份有限公司 | Method for preparing polyester-polyester blocked copolyester |
CN103113561A (en) * | 2011-10-12 | 2013-05-22 | 苏州莫立克新型材料有限公司 | Fast degradable polyester polymer and preparation method and use thereof |
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2016
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Publication number | Priority date | Publication date | Assignee | Title |
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CN103113561A (en) * | 2011-10-12 | 2013-05-22 | 苏州莫立克新型材料有限公司 | Fast degradable polyester polymer and preparation method and use thereof |
CN102516517A (en) * | 2011-12-13 | 2012-06-27 | 金发科技股份有限公司 | Method for preparing polyester-polyester blocked copolyester |
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