CN106008932A - Novel method for preparing poly(butylene succinate) through melt polycondensation - Google Patents
Novel method for preparing poly(butylene succinate) through melt polycondensation Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 poly(butylene succinate) Polymers 0.000 title claims abstract description 21
- 238000006068 polycondensation reaction Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 229920002961 polybutylene succinate Polymers 0.000 claims description 30
- 239000004631 polybutylene succinate Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000001384 succinic acid Substances 0.000 claims description 14
- 230000008901 benefit Effects 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052756 noble gas Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000008859 change Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000704 biodegradable plastic Polymers 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 101100448366 Arabidopsis thaliana GH3.12 gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A novel method for preparing poly(butylene succinate) through melt polycondensation comprises the following steps: S11, adding 1,4-butanedioic acid and 1,4-butanediol into a reactor, and adding an appropriate amount of rare earth oxide serving as a main catalyst and a Na-X type molecular sieve serving as an assistant catalyst to form a mixture; S12, under the atmosphere of inert gas, rapidly raising temperature of the mixture under the stirring condition to 160 to 180 DEG C, and conducting reaction for 1 to 3 h; S13, under the vacuum condition, rapidly raising temperature of the product obtained in the step S12 to 200 to 240 DEG C, and stirring to conduct reaction for 1 to 4 h; S14, collecting the reaction product, taking out the reaction product while the reaction product is at the high temperature, and finally cooling the reaction product to the room temperature.
Description
Technical field
The present invention relates to a kind of new method being prepared poly butylene succinate by melt polycondensation.
Background technology
The white pollution problems of globalization is on the rise, and biodegradable plastic gets more and more people's extensive concerning all the more.Fat
Fat adoption esters macromolecular material has good biocompatibility and degradation property, becomes the main of biodegradable plastic and sends out
Exhibition direction.Wherein, poly butylene succinate (PBS) has become with its good mechanical property and heat resistance and has most had development
The Biodegradable plastics of potentiality.
But, in prior art, a kind of obtained molecular weight of method preparing poly butylene succinate is relatively low, makes acquisition
Poly butylene succinate there is relatively low heat stability.
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, it is provided that one prepares poly-succinic fourth by melt polycondensation
The new method of diol ester.
For solving above-mentioned technical problem, present invention employs techniques below measure:
The present invention provides a kind of new method being prepared poly butylene succinate by melt polycondensation, comprises the following steps:
S11, weighs 1, 4-succinic acid and BDO adds in reactor, and adds suitable rare earth oxide conduct
Major catalyst and Na-X type molecular sieve form mixture as promoter；
S12, under the atmosphere of noble gas, is brought rapidly up described mixture to 160 DEG C～180 under conditions of stirring
DEG C reaction 1～3h；
S13, under vacuum, product step S12 obtained is rapidly increased to 200～240 DEG C, stirring reaction 1-
4h；And
S14, collects distillation reaction product, and takes advantage of high temperature taking-up product, finally product is cooled to room temperature.
For further mature technology scheme, present invention additionally comprises techniques below feature:
As improving further, in step s 11, described 1, 4-succinic acid and described BDO are according to mol ratio
1: 1～1.1 mixing.
As improving further, in step s 12, described noble gas is nitrogen or rare gas.
As improving further, in step s 12, described mixture is brought rapidly up to 170 DEG C under conditions of stirring
Reaction 2h, wherein, the speed of intensification is 10～50 DEG C/min, is preferably, and the speed of intensification is 40～50 DEG C/min.
As improving further, in step s 13, product step S12 obtained is rapidly increased to 220～230 DEG C of steamings
Evaporate reaction 3h.
As improving further, described rare earth oxide is Nd2O3。
As improving further, the air pressure of described vacuum condition is less than or equal to 1kPa.
As improving further, in step s 12, described mixture is brought rapidly up to 170 DEG C under conditions of stirring
Reaction 2h.
Poly butylene succinate that the present invention provides and preparation method thereof has the advantage that one, uses rare earth oxygen
Compound catalyst is major catalyst, and Na-molecular sieve is promoter, can synthesize high molecular with melt-polycondensation the most respectively
Poly butylene succinate so that described poly butylene succinate obtains good heat stability；Its two, the present invention's
Method makes full use of raw material, has good industrial prospect；Its three, the method success rate of the present invention is high, reproducible；Its
Four, also to have synthesis step relatively easy for the method for the present invention, easily realizes, wherein melt-polycondensation in building-up process without
Use organic solvent, environmental protection has superiority, have utilization to be widely popularized.
Accompanying drawing explanation
In the new method being prepared poly butylene succinate by melt polycondensation that Fig. 1 provides for the embodiment of the present invention 1 and 3
The curve chart that PBS viscosity-average molecular weight changes with reaction temperature.
In the new method being prepared poly butylene succinate by melt polycondensation that Fig. 2 provides for the embodiment of the present invention 2 and 4
The curve chart that PBS viscosity-average molecular weight changed with the response time.
Sample P BS3 that Fig. 3-4 provides for the embodiment of the present invention, the infrared spectrum curve of PBS7, PBS13, PBS18.
The nuclear magnetic resonance map of sample P BS 18 that Fig. 5 provides for the embodiment of the present invention.
Sample P BS3 that Fig. 6 provides for the embodiment of the present invention and the thermogravimetric curve of PBS7.
Detailed description of the invention
With detailed description of the invention, the present invention is described in further detail below in conjunction with the accompanying drawings.
The present invention provides the melt polycondensation method of a kind of poly butylene succinate, comprises the following steps:
S11, weighs 1, 4-succinic acid and BDO adds in reactor, and adds suitable rare earth oxide conduct
Major catalyst and Na-X type molecular sieve form mixture as promoter；
S12, under the atmosphere of noble gas, is brought rapidly up described mixture to 160 DEG C～180 under conditions of stirring
DEG C reaction 1～3h；
S13, under vacuum, product step S12 obtained is rapidly increased to 200～240 DEG C, stirring reaction 1-
4h；And
S14, collects distillation reaction product, and takes advantage of high temperature taking-up product, finally product is cooled to room temperature.
In step s 11, described 1, 4-succinic acid and described BDO are preferably according to mol ratio 1: 1～1.1
Mixing, so can avoid described BDO to volatilize in course of reaction and cause productivity to reduce.It is furthermore preferred that described Isosorbide-5-Nitrae-
Succinic acid and described BDO preferably mix according to mol ratio 1: 1.05.Preferably, described rare earth oxide and institute
The mass ratio stating Na-X type molecular sieve is 1: 0～1, it is furthermore preferred that described rare earth oxide and the matter of described Na-X type molecular sieve
Amount ratio 1: 0.5～1.In the present embodiment, the mass ratio of described rare earth oxide and described Na-X type molecular sieve is about 1: 1, thus
Good synergism can be formed.Described rare earth oxide is preferably Nd2O3。
In step s 12, mainly described poly butylene succinate (PBS) is first esterified into molecular weight polymers.Institute
Stating noble gas can be nitrogen or rare gas.Additionally, it is preferred that, described mixture is brought rapidly up under conditions of stirring
To 170 DEG C of reaction 2h.The heating rate being brought rapidly up is 10～30 DEG C/min.Wherein, prepolymerization reaction is:
nHOOCCH2CH2COOH+(n+1)HO(CH2)4OH
H-(O(CH2)4OOC(CH2)2CO)n-O(CH2)4OH+2nH2O
In step s 13, mainly by improving reaction temperature, polycondensation reaction is completed in high vacuum conditions.Due to contracting
In collecting process, the viscosity of polyester gradually steps up, and hydrone is difficult to remove, so needing to steam at reduced pressure conditions solvent, complete
Become polycondensation reaction.Preferably, the air pressure of described vacuum condition is less than or equal to 1kPa.Wherein, polycondensation reaction is:
H-(O(CH2)4OOC(CH2)2CO)n-O(CH2)4OH+
H-(O(CH2)4OOC(CH2)2CO)m-O(CH2)4OH
H-(O(CH2)4OOC(CH2)2CO)m+n-O(CH2)4OH+HO(CH2)4OH
Embodiment 1:
By 1, 4-succinic acid (AS) (9.01g, about 0.1mol), BDO (BD) (12.40g, about 0.105mol) is dilute
Soil oxide (Nd2O3) (0.01g), Na-X type molecular sieve (0.01g) joins in the three neck round bottom flask of 250ml, installs poly-four
Fluorothene stirring rod, distilling apparatus, be sufficiently stirred for down carrying out oil bath, logical nitrogen protection, rapidly it is warming up to 170 DEG C of reactions
2h.Change vacuum distillation apparatus afterwards into, remove nitrogen protection, change vacuum extractor into, oil bath temperature is warming up to the most respectively
200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C and 240 DEG C, isothermal reaction 2h, stop heating, stirring, remove there-necked flask, take advantage of high temperature
Take out product P BS and be cooled to room temperature.Refer to Fig. 1 and table 1, for the viscosity molecular weight by being calculated PBS1-PBS5 sample
And the relation between reaction temperature.From Fig. 1 and table 1 it can be seen that optimal polycondensation reaction temperature is about 220 DEG C.
Table 1 is reaction temperature and PBS viscosity-average molecular weight relation table in embodiment 1
Embodiment 2:
By 1, 4-succinic acid (AS) (9.01g, about 0.1mol), BDO (BD) (12.40g, about 0.105mol) is dilute
Soil oxide (Nd2O3) (0.01g), Na-X type molecular sieve (0.01g) joins in the three neck round bottom flask of 250ml, installs poly-four
Fluorothene stirring rod, distilling apparatus, be sufficiently stirred for down carrying out oil bath, logical nitrogen protection, rapidly it is warming up to 170 DEG C of reactions
2h.Change vacuum distillation apparatus afterwards into, remove nitrogen protection, change vacuum extractor into, oil bath temperature is rapidly increased to 220 DEG C,
Constant temperature reacts 2.0h, 2.5h, 3.0h, 3.5 and 4.0h respectively, stops heating, stirring, removes there-necked flask, takes advantage of high temperature and takes out
Product P BS is cooled to room temperature.Refer to Fig. 2 and table 2, for by be calculated the viscosity molecular weight of PBS11-PBS15 sample with
Relation between reaction temperature.From Fig. 2 and table 2 it can be seen that optimal polycondensation reaction time is about 3h.
Table 2 is response time and PBS viscosity-average molecular weight relation table in embodiment 2
Another embodiment of the present invention also provides for the preparation method that the melt solution of a kind of poly butylene succinate combines,
Comprise the following steps:
S21, weighs 1, 4-succinic acid and BDO adds in reactor, and adds suitable rare earth oxide conduct
Major catalyst, Na-X type molecular sieve form mixture as promoter and solvent；
S22, is brought rapidly up to 135 DEG C～145 DEG C reaction 0.5～2h under conditions of stirring by described mixture；
S23, the solvent in product step S22 obtained steams；
S24, under vacuum, product step S23 obtained is rapidly increased to 200～240 DEG C, distillation reaction 2-
4h；And
S25, collects distillation reaction product, and takes advantage of high temperature taking-up product, finally product is cooled to room temperature.
In the step s 21, described 1, 4-succinic acid and described BDO preferably mix according to mol ratio 1: 1～1.1
Close.It is furthermore preferred that described 1, 4-succinic acid and described BDO preferably mix according to mol ratio 1: 1.05.Described solvent
It is preferably the organic solvent not reacted, e.g., toluene with described 1, 4-succinic acid and described BDO.Preferably, described
The mass ratio of rare earth oxide and described Na-X type molecular sieve is 1: 0～1, it is furthermore preferred that described rare earth oxide and described Na-
The mass ratio 1: 0.5～1 of X-type molecular sieve.In the present embodiment, described rare earth oxide and the mass ratio of described Na-X type molecular sieve
It is about 1: 1, such that it is able to form good synergism.Described rare earth oxide is preferably Nd2O3。
In step S22, at being preferably brought rapidly up to 140 DEG C under conditions of stirring by described mixture, react 1h.
In step s 24, the air pressure of described vacuum condition is less than or equal to 1kPa.
In step s 24, product step S23 obtained is rapidly increased to 220～230 DEG C, distillation reaction 3h.
Embodiment 3:
By 1, 4-succinic acid (SA) (9.01g, about 0.1mol), BDO (BD) (12.40g, about 0.105mol) is dilute
Soil oxide (0.01g, about 2.97 × 10-5Mol), Na-X type molecular sieve (0.01g) and 25ml toluene join three mouthfuls of 250ml
In round-bottomed flask, put into magnetic stir bar, spherical condensation tube and water knockout drum are connected and is arranged on there-necked flask, at 140 DEG C
Lower stirring 1h.Then open water knockout drum piston, solvent toluene is steamed.Remove division box and reflux, change decompression into and steam
Distillation unit.The temperature of oil bath is rapidly increased to respectively 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C and 240 DEG C, by intrinsic pressure minimizing extremely
About 1kPa, the isothermal reaction regular hour, stops heating, stirring, removes there-necked flask, takes out product P BS while hot, treat that it is cold
But seal up for safekeeping standby to room temperature.Refer to Fig. 1 and table 3, for the viscosity molecular weight by being calculated PBS6-PBS10 sample with anti-
Answer the relation between temperature.From Fig. 1 and table 3 it can be seen that optimal polycondensation reaction temperature is about 230 DEG C.
Table 3 is reaction temperature and PBS viscosity-average molecular weight relation table in embodiment 3
Embodiment 4:
By 1, 4-succinic acid (SA) (9.01g, about 0.1mol), BDO (BD) (12.40g, about 0.105mol) is dilute
Soil oxide (0.01g, about 2.97 × 10-5Mol), Na-X type molecular sieve (0.01g) and 25ml toluene join three mouthfuls of 250ml
In round-bottomed flask, put into magnetic stir bar, spherical condensation tube and water knockout drum are connected and is arranged on there-necked flask, at 140 DEG C
Lower stirring 1h.Then open water knockout drum piston, solvent toluene is steamed.Remove division box and reflux, change decompression into and steam
Distillation unit.The temperature of oil bath is rapidly increased to 230 DEG C respectively, by intrinsic pressure minimizing to about 1kPa, isothermal reaction 2.0h, 2.5h,
3.0h, 3.5 and 4.0h, stop heating, stirring, removes there-necked flask, takes out product P BS while hot, treats that it is cooled to room temperature envelope
Deposit standby.Refer to Fig. 1 and table 3, for by being calculated between viscosity molecular weight and the reaction temperature of PBS16-PBS20 sample
Relation.From Fig. 2 and table 4 it can be seen that optimal polycondensation reaction time is about 3.0h.
Table 4 is response time and PBS viscosity-average molecular weight relation table in embodiment 4
Please with reference to Fig. 3-4, Fig. 3-4 is for using NICOCET IS10 type Fourier infrared spectrograph (U.S.'s Buddhist nun's high-tensile strength
Instrument company) test sample PBS3, the infrared spectrum of PBS7, PBS13, PBS18.It can be seen that in two kinds of polymer
Infrared spectrum quite similar.2946cm-1Place is methylene (CH2) stretching vibration absworption peak, 1717cm-1Place is carbonyl (C=
O) stretching vibration absworption peak, 1387cm-1Place is methylene (CH2) bending vibration absworption peak, 1209cm-1And 1156cm-1Place is C-
O stretching vibration absworption peak.Product obtained by the existence of these characteristic absorption peaks proves is expection product PBS.
It is that product P BS 18 is dissolved in 0.5ml deuterochloroform please with reference to Fig. 5, Fig. 5, with AMX200 fourier transform core
Magnetic resonance device detects.
Showing in Fig. 5, having 3 main absworption peaks, chemical shift is δ=1.71 (m, 4H, CH respectively2CH2CH2CH2), δ
=2.65 (t, 4H, OCOCH2), δ=4.09 (t, 4H, CH2OCO), area ratio is about 1: 1: 1, it was demonstrated that sample is PBS.
Please with reference to Fig. 6, Fig. 6 for use NETZSCH STA409PC type thermal analyzer (Germany Nai Chi company) to more than
It is following thermal multigraph that sample P BS3 and PBS7 carry out thermogravimetric analysis measurement result.
From fig. 6 it can be seen that PBS has a certain amount of mass loss between 20～300 DEG C.Quality Down after 315 DEG C
Speed drastically raises, and it is 378 DEG C that weightless ratio reaches the temperature of 50%.In addition, it can be seen that PBS begins with more than 300 DEG C
Bigger mass loss phenomenon.Due to PBS processing and use process temperature not over 200 DEG C, therefore PBS processing and use
During be difficult to thermal decomposition.Illustrate that PBS has good heat stability.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. done, within should be included in the scope of protection of the invention.
Claims (10)
1. prepared a new method for poly butylene succinate by melt polycondensation, comprise the following steps:
S11, weighs 1, 4-succinic acid and BDO adds in reactor, and adds suitable rare earth oxide as sponsoring
Agent and Na-X type molecular sieve form mixture as promoter；
S12, under the atmosphere of noble gas, is brought rapidly up described mixture to 160 DEG C～180 DEG C instead under conditions of stirring
Answer 1～3h；
S13, under vacuum, product step S12 obtained is rapidly increased to 200～240 DEG C, stirring reaction 1-4h；With
And
S14, collects distillation reaction product, and takes advantage of high temperature taking-up product, finally product is cooled to room temperature.
Method the most according to claim 1, it is characterised in that: in step s 11, described 1, 4-succinic acid and described 1,
4-butanediol mixes according to mol ratio 1: 1～1.1.
Method the most according to claim 2, it is characterised in that: in step s 11, described 1, 4-succinic acid and described 1,
4-butanediol mixes according to mol ratio 1: 1.05.
Method the most according to claim 1, it is characterised in that: in step s 12, described noble gas is nitrogen or rare
Gas.
Method the most according to claim 1, it is characterised in that: in step s 12, by described mixture in the condition stirred
Under be brought rapidly up to 170 DEG C reaction 2h.
Method the most according to claim 1, it is characterised in that: in step s 13, product step S2 obtained is rapid
Rise to 220～230 DEG C of distillation reaction 3h.
Method the most according to claim 1, it is characterised in that: described rare earth oxide is Nd2O3。
Method the most according to claim 1, it is characterised in that: the air pressure of described vacuum condition is less than or equal to 1kPa.
Method the most according to claim 1, it is characterised in that: in step s 12, by described mixture in the condition stirred
Under be brought rapidly up to 170 DEG C reaction 2h.
Method the most according to claim 1, it is characterised in that: described rare earth oxide and described Na-X type molecular sieve
Mass ratio is 1: 0～1.
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