CN106008932B - The method that poly butylene succinate is prepared by melt polycondensation - Google Patents
The method that poly butylene succinate is prepared by melt polycondensation Download PDFInfo
- Publication number
- CN106008932B CN106008932B CN201610568940.XA CN201610568940A CN106008932B CN 106008932 B CN106008932 B CN 106008932B CN 201610568940 A CN201610568940 A CN 201610568940A CN 106008932 B CN106008932 B CN 106008932B
- Authority
- CN
- China
- Prior art keywords
- reaction
- succinic acid
- reaction product
- stirring
- butylene succinate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002961 polybutylene succinate Polymers 0.000 title claims abstract description 37
- 239000004631 polybutylene succinate Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 21
- -1 poly butylene succinate Polymers 0.000 title claims abstract description 19
- 238000006068 polycondensation reaction Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 23
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 15
- 239000001384 succinic acid Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 14
- 230000008901 benefit Effects 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000003426 co-catalyst Substances 0.000 abstract description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000006872 improvement Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 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
- 238000010792 warming Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 238000009434 installation Methods 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
- 238000010992 reflux Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction 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
- 238000010521 absorption reaction Methods 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
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction 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
- 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
- 238000012545 processing Methods 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
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 kind of new method that poly butylene succinate is prepared by melt polycondensation, comprises the following steps：S11, weighs Isosorbide-5-Nitrae succinic acid and Isosorbide-5-Nitrae butanediol is added in reactor, and adds appropriate rare earth oxide and form mixture as co-catalyst as major catalyst and Na X-type molecular sieves；S12, under the atmosphere of inert gas, the mixture is brought rapidly up under conditions of stirring to 160 DEG C~180 DEG C 1~3h of reaction；S13, under vacuum, is rapidly increased to 200~240 DEG C, 1 4h of stirring reaction by the step S12 products obtained；And S14, collecting reaction product, and take advantage of high temperature and take out reaction product, finally reaction product is cooled to room temperature.
Description
Technical field
The present invention relates to a kind of new method that poly butylene succinate is prepared by melt polycondensation.
Background technology
The white pollution problems of globalization are on the rise, and biodegradable plastic gets more and more people's extensive concerning all the more.Fat
Fat adoption esters high molecular material has good biocompatibility and degradation property, becomes the main hair of biodegradable plastic
Open up direction.Wherein, poly butylene succinate (PBS) is become and most developed with its good mechanical property and heat resistance
The Biodegradable plastics of potentiality.
However, to obtain molecular weight relatively low for a kind of method for preparing poly butylene succinate in the prior art, make acquisition
Poly butylene succinate there is relatively low heat endurance.
The content of the invention
The shortcomings that it is an object of the invention to overcome the prior art, there is provided one kind prepares poly-succinic fourth by melt polycondensation
The new method of diol ester.
In order to solve the above technical problems, present invention employs following technical measures：
The present invention provides a kind of new method that poly butylene succinate is prepared by melt polycondensation, comprises the following steps：
S11, weighs 1, 4- succinic acid and 1,4-butanediol is added in reactor, and adds appropriate rare earth oxide conduct
Major catalyst and Na-X types molecular sieve form mixture as co-catalyst；
S12, under the atmosphere of inert gas, the mixture is brought rapidly up under conditions of stirring to 160 DEG C~180
DEG C reaction 1~3h；
S13, under vacuum, is rapidly increased to 200~240 DEG C, stirring reaction 1- by the step S12 products obtained
4h；And
S14, collects distillation reaction product, and takes advantage of high temperature and take out reaction product, is finally cooled to room temperature reaction product.
For further mature technology scheme, present invention additionally comprises following technical characteristic：
As a further improvement, in step s 11, the 1, 4- succinic acid and the 1,4-butanediol are according to molar ratio
1: 1~1.1 mixing.
As a further improvement, in step s 12, the inert gas is nitrogen or rare gas.
As a further improvement, in step s 12, the mixture is brought rapidly up under conditions of stirring to 170 DEG C
2 h are reacted, wherein, the speed of heating is 10~50 DEG C/min, is preferably, the speed of heating is 40~50 DEG C/min.
As a further improvement, in step s 13, the step S12 products obtained are rapidly increased to 220~230 DEG C of steamings
Evaporate reaction 3h.
As a further improvement, the rare earth oxide is Nd2O3。
As a further improvement, the air pressure of the vacuum condition is less than or equal to 1kPa.
As a further improvement, in step s 12, the mixture is brought rapidly up under conditions of stirring to 170 DEG C
React 2 h.
Poly butylene succinate provided by the invention and preparation method thereof has the following advantages：First, using rare earth oxygen
Compound catalyst is major catalyst, and Na- molecular sieves are co-catalyst, then can synthesize high molecular weight with melt-polycondensation respectively
Poly butylene succinate so that the poly butylene succinate obtains good heat endurance；Second, the present invention
Method makes full use of raw material, has good industrial prospect；Third, the method success rate of the present invention is high, it is reproducible；Its
4th, method of the invention is also relatively easy with synthesis step, and easy to implement, wherein melt-polycondensation in the synthesis process need not
Organic solvent is used, it is advantageous in environmental protection, there is utilization to be widely popularized.
Brief description of the drawings
Fig. 1 is in the new method that poly butylene succinate is prepared by melt polycondensation that the embodiment of the present invention 1 and 3 provides
The curve map that PBS viscosity average molecular weighs change with reaction temperature.
Fig. 2 is in the new method that poly butylene succinate is prepared by melt polycondensation that the embodiment of the present invention 2 and 4 provides
The curve map that PBS viscosity average molecular weighs change with the reaction time.
Fig. 3-4 is the infrared spectrum curve of sample P BS3, PBS7, PBS13, PBS18 provided in an embodiment of the present invention.
Fig. 5 is the nuclear magnetic resonance map of sample P BS 18 provided in an embodiment of the present invention.
Fig. 6 is the thermogravimetric curve of sample P BS3 and PBS7 provided in an embodiment of the present invention.
Embodiment
The present invention is described in further detail with embodiment below in conjunction with the accompanying drawings.
The present invention provides a kind of melt polycondensation method of poly butylene succinate, comprises the following steps：
S11, weighs 1, 4- succinic acid and 1,4-butanediol is added in reactor, and adds appropriate rare earth oxide conduct
Major catalyst and Na-X types molecular sieve form mixture as co-catalyst；
S12, under the atmosphere of inert gas, the mixture is brought rapidly up under conditions of stirring to 160 DEG C~180
DEG C reaction 1~3h；
S13, under vacuum, is rapidly increased to 200~240 DEG C, stirring reaction 1- by the step S12 products obtained
4h；And
S14, collects distillation reaction product, and takes advantage of high temperature and take out reaction product, is finally cooled to room temperature reaction product.
In step s 11, the 1, 4- succinic acid and the 1,4-butanediol are preferably according to molar ratio 1: 1~1.1
Mixing, can so volatilize during the reaction to avoid the 1,4-butanediol causes yield to reduce.It is furthermore preferred that the Isosorbide-5-Nitrae-
Succinic acid and the 1,4-butanediol are preferably mixed according to molar ratio 1: 1.05.Preferably, the rare earth oxide and institute
The mass ratio for stating Na-X type molecular sieves is 1: 0~1, it is furthermore preferred that the matter of the rare earth oxide and the Na-X types molecular sieve
Measure ratio 1: 0.5~1.In the present embodiment, the mass ratio of the rare earth oxide and the Na-X types molecular sieve is about 1: 1, so that
Good synergistic effect can be formed.The rare earth oxide is preferably Nd2O3。
In step s 12, the poly butylene succinate (PBS) is first mainly esterified into molecular weight polymers.Institute
It can be nitrogen or rare gas to state inert gas.Additionally, it is preferred that, the 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, polycondensation reaction is mainly completed in high vacuum conditions by improving reaction temperature.Due to contracting
In collecting process, the viscosity of polyester gradually steps up, and hydrone is difficult to remove, so need to steam solvent at reduced pressure conditions, it is complete
Into polycondensation reaction.Preferably, the air pressure of the 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：
1, 4- succinic acid (AS) (9.01g, about 0.1mol), 1,4-butanediol (BD) (12.40g, about 0.105mol) is dilute
Native oxide (Nd2O3) (0.01g), Na-X types molecular sieve (0.01g) is added in the three neck round bottom flask of 250ml, installation poly- four
Vinyl fluoride stirring rod, distilling apparatus, are sufficiently stirred lower carry out oil bath, lead to nitrogen protection, are warming up to 170 DEG C of reactions to it rapidly
2h.Change vacuum distillation apparatus into afterwards, remove nitrogen protection, be changed to vacuum extractor, oil bath temperature is warming up to rapidly respectively
200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C and 240 DEG C, isothermal reaction 2h, stop heating, stirring, remove three-necked flask, take advantage of high temperature
Product PBS is taken out to be cooled to room temperature.Fig. 1 and table 1 are referred to, for the viscosity molecular weight of PBS1-PBS5 samples is obtained by calculation
Relation between reaction temperature.From Fig. 1 and table 1 as can be seen that optimal polycondensation reaction temperature is 220 DEG C or so.
Table 1 is reaction temperature and PBS viscosity average molecular weigh relation tables in embodiment 1
Embodiment 2：
1, 4- succinic acid (AS) (9.01g, about 0.1mol), 1,4-butanediol (BD) (12.40g, about 0.105mol) is dilute
Native oxide (Nd2O3) (0.01g), Na-X types molecular sieve (0.01g) is added in the three neck round bottom flask of 250ml, installation poly- four
Vinyl fluoride stirring rod, distilling apparatus, are sufficiently stirred lower carry out oil bath, lead to nitrogen protection, are warming up to 170 DEG C of reactions to it rapidly
2h.Change vacuum distillation apparatus into afterwards, remove nitrogen protection, be changed to vacuum extractor, 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 three-necked flask, takes advantage of high temperature taking-up
Product PBS is cooled to room temperature.Refer to Fig. 2 and table 2, for be obtained by calculation the viscosity molecular weight of PBS11-PBS15 samples with
Relation between reaction temperature.From Fig. 2 and table 2 as can be seen that optimal polycondensation reaction time is 3h or so.
Table 2 is reaction time and PBS viscosity average molecular weigh relation tables in embodiment 2
Another embodiment of the present invention also provides the preparation method that a kind of melt solution of poly butylene succinate is combined,
Comprise the following steps：
S21, weighs 1, 4- succinic acid and 1,4-butanediol is added in reactor, and adds appropriate rare earth oxide conduct
Major catalyst, Na-X types molecular sieve form mixture as co-catalyst and solvent；
S22, the mixture is brought rapidly up to 0.5~2h of reaction at 135 DEG C~145 DEG C under conditions of stirring；
S23, the solvent in step S22 the resulting products is steamed；
S24, under vacuum, is rapidly increased to 200~240 DEG C, distillation reaction 2- by the step S23 products obtained
4h；And
S25, collects distillation reaction product, and takes advantage of high temperature and take out reaction product, is finally cooled to room temperature reaction product.
In the step s 21, the 1, 4- succinic acid and the 1,4-butanediol are preferably mixed according to molar ratio 1: 1~1.1
Close.It is furthermore preferred that the 1, 4- succinic acid and the 1,4-butanediol are preferably mixed according to molar ratio 1: 1.05.The solvent
The organic solvent not reacted with the 1, 4- succinic acid and the 1,4-butanediol preferably, e.g., toluene.Preferably, it is described
The mass ratio of rare earth oxide and the Na-X types molecular sieve is 1: 0~1, it is furthermore preferred that the rare earth oxide and the Na-
The mass ratio 1: 0.5~1 of X-type molecular sieve.In the present embodiment, the mass ratio of the rare earth oxide and the Na-X types molecular sieve
About 1: 1, so as to form good synergistic effect.The rare earth oxide is preferably Nd2O3。
In step S22, it is brought rapidly up under conditions of stirring reacting 1h at 140 DEG C preferably by the mixture.
In step s 24, the air pressure of the vacuum condition is less than or equal to 1kPa.
In step s 24, the step S23 products obtained are rapidly increased to 220~230 DEG C, distillation reaction 3h.
Embodiment 3：
1, 4- succinic acid (SA) (9.01g, about 0.1mol), 1,4-butanediol (BD) (12.40g, about 0.105mol) is dilute
Native oxide (0.01g, about 2.97 × 10-5Mol), Na-X types molecular sieve (0.01g) and 25ml toluene are added to three mouthfuls of 250ml
In round-bottomed flask, magnetic stir bar is put into, spherical condensation tube is connected with water knockout drum and is installed on three-necked flask, at 140 DEG C
Lower stirring 1h.Then water knockout drum piston is opened, solvent toluene is steamed.Division box and reflux are removed, decompression is changed to and steams
Distillation unit.The temperature of oil bath is rapidly increased to 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C and 240 DEG C respectively, by internal pressure reduce to
1kPa or so, the isothermal reaction regular hour, stops heating, stirring, removes three-necked flask, take out product PBS while hot, treat that its is cold
But sealed up for safekeeping to room temperature spare.Refer to Fig. 1 and table 3, for be obtained by calculation the viscosity molecular weight of PBS6-PBS10 samples with it is anti-
Answer the relation between temperature.From Fig. 1 and table 3 as can be seen that optimal polycondensation reaction temperature is 230 DEG C or so.
Table 3 is reaction temperature and PBS viscosity average molecular weigh relation tables in embodiment 3
Embodiment 4：
1, 4- succinic acid (SA) (9.01g, about 0.1mol), 1,4-butanediol (BD) (12.40g, about 0.105mol) is dilute
Native oxide (0.01g, about 2.97 × 10-5Mol), Na-X types molecular sieve (0.01g) and 25ml toluene are added to three mouthfuls of 250ml
In round-bottomed flask, magnetic stir bar is put into, spherical condensation tube is connected with water knockout drum and is installed on three-necked flask, at 140 DEG C
Lower stirring 1h.Then water knockout drum piston is opened, solvent toluene is steamed.Division box and reflux are removed, decompression is changed to and steams
Distillation unit.The temperature of oil bath is rapidly increased to 230 DEG C respectively, internal pressure is reduced to 1kPa or so, isothermal reaction 2.0h, 2.5h,
3.0h, 3.5 and 4.0h, stop heating, stirring, remove three-necked flask, take out product PBS while hot, treat that it is cooled to room temperature envelope
Deposit spare.Fig. 1 and table 3 are referred to, to be obtained by calculation between the viscosity molecular weight of PBS16-PBS20 samples and reaction temperature
Relation.From Fig. 2 and table 4 as can be seen that optimal polycondensation reaction time is 3.0h or so.
Table 4 is reaction time and PBS viscosity average molecular weigh relation tables in embodiment 4
Please with reference to Fig. 3-4, Fig. 3-4 is to use NICOCET IS10 type Fourier infrared spectrograph (U.S. Buddhist nun high-tensile strengths
Instrument company) test sample PBS3, PBS7, PBS13, PBS18 infrared spectrum.It can be seen from the figure that in two kinds of polymer
Infrared spectrum it is quite similar.2946cm-1Locate as methylene (CH2) stretching vibration absworption peak, 1717cm-1Locate as carbonyl (C=
O) stretching vibration absworption peak, 1387cm-1Locate as methylene (CH2) flexural vibrations absworption peak, 1209cm-1And 1156cm-1Locate be
C-O stretching vibration absworption peaks.The presence of these characteristic absorption peaks proves that obtained product is expected product PBS.
Please with reference to Fig. 5, Fig. 5 is dissolved in 0.5ml deuterochloroforms for product PBS 18, with AMX200 Fourier transform cores
Magnetic resonance device detects.
Show there are 3 main absworption peaks in Fig. 5, chemical shift is δ=1.71 (m, 4H, CH respectively2CH2CH2CH2), δ
=2.65 (t, 4H, OCOCH2), δ=4.09 (t, 4H, CH2OCO), area is than about 1: 1: 1, it was demonstrated that sample PBS.
Please with reference to Fig. 6, Fig. 6 is to the above using NETZSCH STA409PC types thermal analyzer (German Nai Chi companies)
It is following thermal multigraph that sample P BS3 and PBS7, which 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.Decline from quality after 315 DEG C
Speed drastically raises, and the temperature that weightless ratio reaches 50% is 378 DEG C.In addition, it can be seen that PBS is begun with more than 300 DEG C
Larger mass loss phenomenon.Due to the processing of PBS and using process temperature not over 200 DEG C, PBS is being processed and used
During be not easy to thermally decompose.Illustrate that PBS has good heat endurance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God and any modification, equivalent substitution, improvement and etc. within principle, done, should be included within the scope of protection of the invention.
Claims (5)
1. a kind of method that poly butylene succinate is prepared by melt polycondensation, comprises the following steps：
S11, weighs 1, 4- succinic acid, 1,4-butanediol, Nd2O3, Na-X types molecular sieve add reactor in, obtain mixture, institute
State Nd2O3Mass ratio with the Na-X types molecular sieve is 1:1, and Nd2O3Mass ratio with the 1, 4- succinic acid is 1:901；
S12, under the atmosphere of inert gas, the mixture is brought rapidly up under conditions of stirring to 170 DEG C of reaction 2h, its
In, heating rate is 10~30 DEG C/min；
S13, under vacuum, is rapidly increased to 220 DEG C, stirring reaction 2h by the step S12 products obtained；And
S14, collects distillation reaction product, and takes advantage of high temperature and take out reaction product, is finally cooled to room temperature reaction product.
2. according to the method described in claim 1, it is characterized in that：In step s 11, the 1, 4- succinic acid and described 1,
4- butanediols are mixed according to molar ratio 1: 1~1.1.
3. according to the method described in claim 2, it is characterized in that：In step s 11, the 1, 4- succinic acid and described 1,
4- butanediols are mixed according to molar ratio 1: 1.05.
4. according to the method described in claim 1, it is characterized in that：In step s 12, the inert gas is nitrogen or rare
Gas.
5. according to the method described in claim 1, it is characterized in that：The air pressure of the vacuum condition is less than or equal to 1kPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610568940.XA CN106008932B (en) | 2016-07-19 | 2016-07-19 | The method that poly butylene succinate is prepared by melt polycondensation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610568940.XA CN106008932B (en) | 2016-07-19 | 2016-07-19 | The method that poly butylene succinate is prepared by melt polycondensation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106008932A CN106008932A (en) | 2016-10-12 |
| CN106008932B true CN106008932B (en) | 2018-04-20 |
Family
ID=57115727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610568940.XA Active CN106008932B (en) | 2016-07-19 | 2016-07-19 | The method that poly butylene succinate is prepared by melt polycondensation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106008932B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3342578B2 (en) * | 1994-07-13 | 2002-11-11 | ユニチカ株式会社 | Method for producing aliphatic polyester |
| CN1239563C (en) * | 2001-12-12 | 2006-02-01 | 中国科学院理化技术研究所 | Method for preparing poly (butylene succinate) |
| JP4248999B2 (en) * | 2003-12-01 | 2009-04-02 | 三菱化学株式会社 | Method for producing aliphatic polyester |
| CN100562537C (en) * | 2007-06-26 | 2009-11-25 | 四川大学 | High molecular weight poly (butylene succinate) and preparation method thereof |
| CN101328261B (en) * | 2008-07-29 | 2011-01-12 | 南京工业大学 | Preparation method of high molecular weight poly (butylene succinate) |
| CN102718949B (en) * | 2012-07-09 | 2014-02-12 | 旭阳化学技术研究院有限公司 | Preparation method of polybutylene succinate |
| CN104693428B (en) * | 2015-03-17 | 2016-09-28 | 江苏钟腾化工有限公司 | The preparation method of the poly butylene succinate of high molecular |
-
2016
- 2016-07-19 CN CN201610568940.XA patent/CN106008932B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106008932A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zeng et al. | Curing behavior of epoxidized soybean oil with biobased dicarboxylic acids | |
| Brocas et al. | Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate‐free polyurethane networks | |
| CN102575029B (en) | Polyester films with improved oil repellency | |
| Zhang et al. | Environment-friendly synthesis and performance of a novel hyperbranched epoxy resin with a silicone skeleton | |
| Li et al. | Bio-based shape memory epoxy resin synthesized from rosin acid | |
| Li et al. | Synthesis, characterization of a rosin-based epoxy monomer and its comparison with a petroleum-based counterpart | |
| EP2172446A1 (en) | In situ synthesis of ester-amide-containing molecules | |
| CN108610323A (en) | A kind of preparation method of lactide | |
| EP3134459A1 (en) | Aliphatic polyimides from a 1:2 molar ratio of diamine and unsaturated monoanhydride or unsaturated diacid | |
| CN112831041B (en) | Terephthalic acid type unsaturated polyester and preparation method thereof | |
| Ecochard et al. | Linseed oil‐based thermosets by Aza‐Michael polymerization | |
| CN104937007A (en) | Crosslinkable polyketal esters, methods of manufacture and uses thereof | |
| Xu et al. | An ambient-cured coating film obtained via a Knoevenagel and Michael addition reactions based on modified acetoacetylated castor oil prepared by a thiol-ene coupling reaction | |
| Jaswal et al. | Structure-property correlation study of bio-based multifunctional vinyl ester resin in presence of methacrylated lignin model compounds | |
| CN107189049B (en) | A kind of hydridization type polyester and preparation method thereof | |
| CN104231235A (en) | Preparation method of hyperbranched polyester with flexible long chain | |
| CN111978444B (en) | Organic polyacid-based photocuring resin and preparation method and application thereof | |
| CN106008932B (en) | The method that poly butylene succinate is prepared by melt polycondensation | |
| Bu et al. | Fully bio-based epoxy resins derived from magnolol and varying furan amines: Cure kinetics, superior mechanical and thermal properties | |
| CN110256657A (en) | A kind of aliphatic-aromatic copolyester and preparation method thereof | |
| CN106715526B (en) | It is used to prepare the ad hoc approach of biology base polyester | |
| CN105566618A (en) | Modified poly(butylene succinate) and preparation method thereof | |
| CN106146813B (en) | Solution is combined the method for preparing poly butylene succinate with melt polycondensation | |
| CN110467726B (en) | High-melting-point bio-based polyesteramide and preparation method thereof | |
| Qu et al. | Thermoset polyimide matrix resins with improved toughness and high Tg for high temperature carbon fiber composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201113 Address after: 213000 No. 1228 Changjiang North Road, Xinbei District, Changzhou, Jiangsu Patentee after: CHANGMAO BIOCHEMICAL ENGINEERING Co.,Ltd. Address before: 352100, No. 98-1 South Jiaocheng Road, Chengnan Town, Jiaocheng District, Fujian, Ningde Patentee before: NINGDE NORMAL University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231019 Address after: No. 8 Tashan Street, Changxing Island Economic Zone, Dalian City, Liaoning Province, 116000 Patentee after: Changmao (Dalian) New Materials Co.,Ltd. Address before: 213000 No. 1228, Changjiang North Road, Xinbei District, Changzhou City, Jiangsu Province Patentee before: CHANGMAO BIOCHEMICAL ENGINEERING Co.,Ltd. |
|
| TR01 | Transfer of patent right |