CN101724141A - Method for preparing high molecular weight-controlled polybuthylenesuccinate - Google Patents
Method for preparing high molecular weight-controlled polybuthylenesuccinate Download PDFInfo
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- CN101724141A CN101724141A CN200810172340A CN200810172340A CN101724141A CN 101724141 A CN101724141 A CN 101724141A CN 200810172340 A CN200810172340 A CN 200810172340A CN 200810172340 A CN200810172340 A CN 200810172340A CN 101724141 A CN101724141 A CN 101724141A
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Abstract
The invention belongs to the field of preparation of polyesters, and in particular to a method for preparing a polybuthylenesuccinate (PBS) with a viscosity-average molecular weight between 1,000 and 60,000 by two reaction steps of solution polycondensation and crosslinking. The prepared PBS-based plastic has excellent processability, has higher tensile strength and elongation at break than the PBS which is prepared by direct polycondensation, and simultaneously has excellent hue and texture. The preparation method for the polybuthylenesuccinate comprises the following steps: firstly, adopting 1,4-butanediol and butanedioic acid as raw materials to producing PBS oligomer with a lower molecular weight by the solution polycondensation under the action of a catalyst of which the dosage is 0.1/600 to 5/600 mol of that of the butanedioic acid, wherein the temperature range of the polycondensation is between 120 and 235 DEG C; and then crosslinking between molecules by a certain silane binder, and performing the crosslinking reaction at the temperature of between 30 and 180 DEG C for 0.5 to 30 hours to prepare the PBS with the controllable molecular weight between 1,000 and 60,000, wherein based on 30 weight parts of polyester prepolymer, the dosage of the binder is 0.1 to10 parts; and a solvent is chlorohydrocarbon, arene and the like. The preparation method has lower requirement on instruments and equipment, so the method for preparing the high molecular weight PBS is simplified and high-efficiency; and the method can synthesize the molecular weight-controlled PBS so as to expand the application fields of the PBS.
Description
Technical field
The invention belongs to preparation polyester process field, be specifically related to a kind ofly through solution polycondensation, two steps of reaction of building bridge are prepared the method for viscosity-average molecular weight at the poly butylene succinate (PBS) of 1000-60000.Prepared PBS base plastic working excellent property, its tensile strength and elongation at break all increase than the PBS that makes by direct polycondensation method, have good color tone and texture simultaneously, and have the molecular weight controllability.
Background technology
In recent years, " white pollution " problem that is caused by plastics more and more is subjected to people's attention.Therefore, the research of various environment-friendly materials and application have obtained paying attention to widely, and the development of fully biodegradable plastics and application have become the research focus in the worldwide.
Aliphatic polyester be can complete biodegradable polymkeric substance, it can eventual degradation become materials such as carbonic acid gas and water under the effect of bacterium or enzyme, environmental sound because its biological degradability and economy, has become the focus of domestic and international research.But adopt the prepared aliphatic polyester of polycondensation still to fail to use as plastics separately at present, major cause is that their fusing point mostly is lower than 100 ℃.Generally, the fusing point of polyester only is higher than 100 ℃, and after forming process, the plastics that obtain just have use value.Poly butylene succinate (PBS) is with respect to other aliphatic polyesters; fusing point and intensity are all than higher; so its most possibly replaces other existing non-biodegradation plastics and becomes a kind of novel universal material; with regard to Application Areas; PBS can be used as the packing plastics of degradability, bio-medical material of degradability (as medical device etc.) etc.; meet the requirement of the environment protection and the strategy of sustainable development, be widely used, promise well.
PBS still is a kind of typical hemicrystalline thermoplastics, and compared with low-density polyethylene, it has good processing properties, elasticity and intensity.Now just extensively be subjected to people's attention.Its multipolymer and blend are just getting more and more and are being developed research.
But there are a series of difficult points in the synthetic method of poly butylene succinate at present, and for example, because esterification is reversible reaction, the equilibrium constant is little, and the existence of low molecule by product is very big to the influence of molecular weight; Decarboxylation takes place easily under comparatively high temps, cyclisation, side reactions such as thermal destruction, thus the poly butylene succinate that obtains often molecular weight is lower, general weight-average molecular weight is several thousand to 10,000, performance can not satisfy actual service requirements, must further improve molecular weight.
In order to prepare the high-molecular weight poly butylene succinate, Chinese scholars has been explored a lot of methods, as DAE KYUNG SONG, people (Journal of Applied Polymer Science such as YONG KIEL SUNG, 1995 Vol.56,1381-1395) adopt solution polymerization process reaction 20h to prepare number-average molecular weight at 16000 poly butylene succinate, but the molecular weight of this product is still not high, and for example patent CN1424339 discloses employing Succinic Acid and butyleneglycol at 160 ℃ of normal pressure esterification 3-4h, add organotin and cadmium acetate then step by step as catalyzer, polycondensation 9h has prepared the weight average molecule 137000 under the high temperature high vacuum, and molecular weight distribution is the synthesis technique of 1.9 poly butylene succinate.Though this technology has made the high-molecular weight poly butylene succinate, technology is comparatively complicated, needs gradation in batches to add catalyzer, and the reaction times is also longer, and cost is higher.Institute of Chemistry, Academia Sinica is with Succinic Acid, 1; 4-butyleneglycol in molar ratio 1: 1-4 mixes; every 163g Succinic Acid, 1 in the reactor; the mixture of 4-butyleneglycol adds 4-20g maleopimaric acid imidodicarboxylic acid ester oligomer; under protection of inert gas; in 160-200 ℃ of following heated and stirred reaction; with cadmium acetate, zinc acetate, antimonous oxide, butyl (tetra) titanate or their any mixture as catalyzer; 0.1%-3% by the quality that always feeds intake puts in the reactor, and polymerization obtains modified butanediol ester poly succinic acid under 230-280 ℃, 5-10Pa.This polymkeric substance has good elongation at break.It is the direct polycondensation method (application number 01144133.X) that monomer prepares poly butylene succinate with butyleneglycol and Succinic Acid that people such as Wang Xiaoqing propose a kind of.Succinic Acid and butyleneglycol are placed reaction unit, wherein, the mole ratio of Succinic Acid and butyleneglycol is 1-3: 1, in temperature is to carry out the normal pressure esterification reaction under 150-200 ℃, be 200-280 ℃ in temperature then, and in the presence of catalyzer, be decompressed to the 10-100Pa polycondensation and obtain poly butylene succinate; Wherein, catalyst consumption is the 0.01%-5% of Succinic Acid mole number.The poly butylene succinate that this invention is prepared, weight-average molecular weight can reach 100,000, is thermoplastic resin, has good mechanical properties, but to the requirement of equipment than higher, cost is higher.
Another kind of raising molecular weight ratio is the chain extension method than effective means.About the chain extension legal system be equipped with the high-molecular weight poly butylene succinate more successful be the clear and macromolecular material company of Japan.The said firm's employing number-average molecular weight is at least 10000 poly butylene succinate as prepolymer, with vulcabond as chainextender, prepared the high-molecular weight poly butylene succinate by frit reaction, its patent (US5391644, US5348700, US5525409) disclosed concrete preparation technology is as follows: at first with Succinic Acid and 1, the 4-butyleneglycol was 190-210 ℃ of normal pressure esterification 3.5 hours, then at 190-210 ℃, polycondensation 3.5hr under the 2-20mmHg vacuum degree condition, obtaining number-average molecular weight is 16800, weight-average molecular weight is 43600 Succinic Acid butyleneglycol prepolymer, react 1hr with this prepolymer and vulcabond under 180-200 ℃ of condition again and make number-average molecular weight as 35000, weight-average molecular weight is 170000 poly butylene succinate product, but because this product molecular weight distribution wide (4.8), its intensity is limited, and its production cycle is long, and cost is higher, greatly limits its use range.People such as Zhao Jingbo propose a kind of method that adopts two-step approach to prepare high-molecular aliphatic polyester (application number 200510093775.9), at first carry out melt phase polycondensation by dibasic alcohol and diprotic acid, the preparation number-average molecular weight 2000～7000 or limiting viscosity at the low molecular weight hydroxy-terminated estrodur performed polymer below 0.5; Carry out chain extension, the preparation aliphatic polyester with two lactan of aliphatics diacyl or the two lactan of aromatic series diacyl again.People such as Wang Yuzhong with both-end hydroxy-butanedioic acid butanediol ester especially lower molecular weight both-end hydroxy-butanedioic acid butanediol ester as prepolymer, lower with 0.1～13% chainextender vulcabond frit reaction preparation cost, molecular weight is high and the poly butylene succinate (application number 200710049370.4) of narrow molecular weight distribution, mechanical property excellence, but the toxicity of vulcabond is bigger, harmful, reduce the use range of PBS to a great extent, limited its application.
Summary of the invention
Primary and foremost purpose of the present invention provides a kind of with short production cycle, the method for preparing poly butylene succinate that cost is low.The PBS molecular weight that this method makes is controlled, the mechanical property excellence.Have good color tone and texture simultaneously.The method of this production controllable molecular weight PBS has been widened its use field greatly.
Technical scheme of the present invention: at first by Succinic Acid and 1, the solution polycondensation reaction of 4-butyleneglycol, the PBS oligopolymer of preparation terminal hydroxy group or end carboxyl carries out intermolecular bridge formation with binding agent to the PBS oligopolymer again, prepares viscosity-average molecular weight and be the poly butylene succinate between 1000-60000.
The present invention at first presses proper proportion with diprotic acid and dibasic alcohol, in the presence of catalyzer, in certain temperature range, prepares low-molecular-weight estrodur performed polymer through solution polycondensation.The 0.1/600-5/600 of catalyst consumption substrate molar weight.The mol ratio of dibasic alcohol and diprotic acid is at 0.8-3 during polycondensation: between 1, the polycondensation temperature range is between 120-235 ℃, and polycondensation reaction time is 1-12h; Carry out intermolecular bridge formation with binding agent then, wherein the estrodur performed polymer with 30 parts of weight fractions calculates, and the binding agent consumption is between 0.1-10 part, and the bridge formation temperature of reaction is 30-180 ℃.Prepare the PBS between the 1000-60000 behind the reaction 0.5-30h.
The used catalyzer of the present invention is any one in antimony glycol, antimony acetate, titanium dioxide, Mono-n-butyltin, dibutyltin diacetate, stannous octoate, tindichloride, tetrabutyl titanate or the isopropyl titanate, or is wherein any several mixture.Used stablizer is any one in Sodium hexametaphosphate 99, triethyl phosphate, sodium hypophosphite, the polyphosphoric acid, or is wherein any several mixture.
The used binding agent of the present invention is glutaraldehyde, ethylene glycol bis shrink glycidyl ethers, epoxy chloropropane, Y-(2,3 glycidoxies) any one in propyl trimethoxy silicane, Y-aminopropyltriethoxywerene werene, Y-(methacryloxy) propyl trimethoxy silicane, anilinomethyl triethoxysilane, anilinomethyl trimethoxy silane, vulcabond or the ethylene glycol bis glycidyl ether, or be wherein any several mixture.
The solvent of bridge formation reaction is any one in toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), dichlorobenzene, ethylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF) or the ethyl acetate among the present invention, or the mixture of any several solvents.
The present invention prepares the terminal hydroxy group or the terminal carboxyl polyester performed polymer of lower molecular weight or feature viscosity earlier by solution polycondensation, carry out intermolecular bridge formation with binding agent again, preparation PBS.This method has reduced vacuum requirements, and speed of response is fast, and efficient, the preparation method is easy, and the PBS of the different molecular weight that makes has expanded its use range greatly, can be used in food, medicine, industries such as building.
The present invention has the following advantages:
1, adopt solution polycondensation, the reaction conditions gentleness, and the by product that generates is few, and lower to the requirement of plant and instrument, thus the preparation method of high molecular weight PBS is simplified, efficient.
2, because the present invention adopts the especially low-molecular-weight succinic acid-butanediol ester of poly butylene succinate to prepare high molecular weight poly (butylene succinate) as prepolymer, thereby not only can greatly shorten the preparation time of prepolymer, but also prepolymer and caking agent reactive activity have been improved, make whole production period ratio tradition polycondensation method and traditional chain extension method shorten almost half time, reduced the cost of final product from technology.
3, the high molecular weight PBS that obtains of the present invention, narrow molecular weight distribution, thereby have thermotolerance and characteristics such as mechanical property is good, and cost is low can break through the bottleneck that it can not use as general-purpose plastics.Its tensile strength and elongation at break all increase than the PBS that direct melt polycondensation obtains.
4, binding agent used in the present invention is nontoxic, and expansion PBS is in the application in food and medicine field.
5, by the control reaction conditions, can synthesize the PBS of different molecular weight, expanded its Application Areas.
6, technology of the present invention is simple, is easy to grasp and control.
Embodiment
The present invention relates to a kind of method of producing controllable molecular weight PBS, may further comprise the steps:
At first utilize Succinic Acid and butyleneglycol to carry out solution polycondensation, the terminal hydroxy group or the terminal carboxyl polyester performed polymer of preparation lower molecular weight or feature viscosity carry out intermolecular bridge formation with binding agent more earlier, by the control reaction conditions, generate the PBS between the 1000-60000.The mol ratio of dibasic alcohol and diprotic acid is generally at 0.8-3 in the polycondensation process: 1, cross when low or too high when alcohol/sour ratio, and all can influence reaction result, prolong the reaction times.Temperature is between 120-235 ℃ in the polycondensation process.Temperature is crossed low reaction speed and is descended, and too high then side reaction increases.
Diprotic acid and dibasic alcohol are carried out solution polycondensation, and the catalyzer that uses in the polycondensation process is the environmental type catalyzer, meets the U.S. FDA standard, is a kind of effective catalyst nontoxic to human body.Catalyst consumption is the 0.1/600-5/600 of Succinic Acid molar weight.
In addition, polycondensation adds an amount of stablizer, prevents the generation of oxidizing reaction in the polycondensation process.
The consumption of binding agent is between the 0.1/30-10/30 of prepolymer quality, and the consumption of binding agent crosses when low that level of response is low, and the molecular weight of final polyester is low, and cost increased when consumption was too high.
The present invention can adopt rotor agitator or electric mixer when binding agent mixes with low viscous PBS, 20～200 rev/mins of rotating speeds, temperature 30-180 ℃.Temperature is crossed the mobile low of low reaction thing, can not be fully and the binding agent reaction, and temperature is too high to cause the oxidation of product and the generation of side reaction again.
In addition, it is worthy of note that the feature viscosity of the prepolymer that provides in following examples is to adopt the chloroform give solvent, measures in 25 ℃ of constant temperature water baths.The viscosity-average molecular weight of prepolymer is by η=KM
η αObtain.The number-average molecular weight of prepolymer is by titration measuring, promptly measure the acid number of prepolymer earlier according to the chemical industry standard HG/T 2078-95 of the People's Republic of China (PRC), the chemical industry standard HG/T 2079-95 of the People's Republic of China (PRC) measures the hydroxyl value of prepolymer, calculates the number-average molecular weight of prepolymer then.The molecular weight of final product and the employing gel permeation chromatography that distributes thereof obtain; The tensile strength of final product and elongation at break are measured according to international standard GB/T13022-1991 and are obtained.
Bridge formation is reflected under the solution state and carries out, the solvent of bridge formation reaction is any one in toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), dichlorobenzene, ethylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF) or the ethyl acetate, or the mixture of any several solvents, select suitable solvent as required.Adopt organic solvent can improve the uniformity coefficient of reaction.Accurate weighing PBS 1.5g, be made into certain density solution, add a certain amount of binding agent, putting into the thermostatical oil bath after pouring in the flask reacts, attemperation is a set(ting)value, adopt magnetic force to stir, carry out viscosity measurement with Ubbelohde viscometer behind the reaction certain hour, and then converse viscosity-average molecular weight.
According to above-described embodiment, the present invention all can realize, below enumerate preferably embodiment to the detailed description of the invention, but realization of the present invention is not limited to following examples, any those skilled in the art, without departing from the spirit of the invention, various changes and the retouching done all should belong within the scope of the present invention.
Embodiment 1: with mol ratio be 3: 11,4-butyleneglycol and Succinic Acid place reaction unit, adding total amount is the isopropyl titanate of Succinic Acid mole number 0.1/600, the mixture of stannous octoate, and adds micro-polyphosphoric acid, the polycondensation temperature is 120 ℃.Obtain the PBS oligopolymer behind the reaction 1h, its viscosity-average molecular weight is 2250.With 30 parts of PBS oligopolymer that make, be dissolved in the dimethyl sulfoxide (DMSO), add 0.1 part of Y-(methacryloxy) propyl trimethoxy silicane, react 30h down in 30 ℃ of oil baths, the viscosity-average molecular weight of resulting polymers is 5610.
Embodiment 2: with reference to embodiment 1, the mol ratio that changes Succinic Acid and butyleneglycol is 2: 1, and adding total amount is the antimony glycol of Succinic Acid mole number 0.5/600, and adds micro-sodium hypophosphite, and the polycondensation temperature is 150 ℃.Obtain the PBS oligopolymer behind the reaction 3h, its viscosity-average molecular weight is 3165.With 30 parts of PBS oligopolymer that make, be dissolved in the trichloromethane, add 0.5 part of ethylene glycol bis glycidyl ether, react 25h down in 30 ℃ of oil baths, the viscosity-average molecular weight of resulting polymers is 53210.
Other embodiment see Table 1.
Table 1
Claims (7)
1. method for preparing controllable molecular weight poly butylene succinate (PBS), it is characterized in that: at first by Succinic Acid and 1, the solution polycondensation reaction of 4-butyleneglycol, the PBS oligopolymer of preparation terminal hydroxy group or end carboxyl, with binding agent the PBS oligopolymer is carried out intermolecular bridge formation again, prepare viscosity-average molecular weight and be the poly butylene succinate between 1000-60000.
2. according to the described method of claim 1, it is characterized in that its condition and processing step are as follows:
(1) the PBS oligopolymer is synthetic
With 1; 4-butyleneglycol and Succinic Acid are put into reactor; under protection of inert gas, heat up and be stirred to raw material and fully dissolve each other; then in certain temperature range; and under the catalytic condition of catalyzer and stablizer; in certain organic solvent,, generate the PBS oligopolymer of certain molecular weight through solution polycondensation reaction for some time.
(2) bridge formation of PBS oligopolymer reaction
Take by weighing the PBS oligopolymer of certain molecular weight, it is scattered in certain organic solvent, adds a certain amount of binding agent then, in certain temperature range, carry out intermolecular bridge formation reaction for some time, continue in the reaction process to stir, prepare the PBS between the 1000-60000.
3. according to the described method of claim 1, it is characterized in that: the used catalyzer of solution polycondensation is any one in antimony glycol, antimony acetate, titanium dioxide, Mono-n-butyltin, dibutyltin diacetate, stannous octoate, tindichloride, tetrabutyl titanate or the isopropyl titanate, or is wherein any several mixture.Used stablizer is any one in Sodium hexametaphosphate 99, triethyl phosphate, sodium hypophosphite, the polyphosphoric acid, or is wherein any several mixture.
4. according to the described method of claim 1, it is characterized in that: the mol ratio of dibasic alcohol and diprotic acid is at 0.8-3 during solution polycondensation: between 1, catalyst consumption is the 0.1/600-5/600 of Succinic Acid molar weight, and range of reaction temperature is between 120-235 ℃, and the reaction times is 1-12h.
5. according to the described method of claim 1, it is characterized in that: described binding agent is glutaraldehyde, ethylene glycol bis shrink glycidyl ethers, epoxy chloropropane, γ-(2,3 glycidoxies) any one in propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-(methacryloxy) propyl trimethoxy silicane, anilinomethyl triethoxysilane, anilinomethyl trimethoxy silane, vulcabond or the ethylene glycol bis glycidyl ether, or be wherein any several mixture.
6. according to the described method of claim 1, it is characterized in that: the solvent of the reaction of building bridge is any one in toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), dichlorobenzene, ethylene dichloride, trichloromethane, tetracol phenixin, tetrahydrofuran (THF) or the ethyl acetate, or the mixture of any several solvents.
7. according to the described method of claim 1, it is characterized in that: the estrodur performed polymer that reacts with 30 parts of weight fractions of building bridge calculates, and the binding agent consumption carries out in the oil bath that is reflected at 30-180 ℃ of building bridge between 0.1-10 part, reaction 0.5-30h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103476827A (en) * | 2010-11-09 | 2013-12-25 | 佛吉亚汽车内部设备工业公司 | Novel oligomers, method for preparation thereof and use thereof for fluidifying and/or improving the stability of polymeric compositions |
| CN104163914A (en) * | 2014-07-21 | 2014-11-26 | 金晖兆隆高新科技有限公司 | Equipment utilizing maleic anhydride and butylene glycol to prepare multiple products |
| CN116120532A (en) * | 2022-12-28 | 2023-05-16 | 常州瑞华化工工程技术股份有限公司 | Preparation method of poly (butylene succinate) and poly (butylene succinate) |
| CN116836525A (en) * | 2023-08-09 | 2023-10-03 | 东莞市泰彩色料有限公司 | Environment-friendly degradable color master batch and preparation method thereof |
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2008
- 2008-11-03 CN CN200810172340A patent/CN101724141A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103476827A (en) * | 2010-11-09 | 2013-12-25 | 佛吉亚汽车内部设备工业公司 | Novel oligomers, method for preparation thereof and use thereof for fluidifying and/or improving the stability of polymeric compositions |
| CN103476827B (en) * | 2010-11-09 | 2015-11-25 | 佛吉亚汽车内部设备工业公司 | New oligo, its preparation method and it is for fluidization and/or the purposes improving polymer composition stability |
| CN104163914A (en) * | 2014-07-21 | 2014-11-26 | 金晖兆隆高新科技有限公司 | Equipment utilizing maleic anhydride and butylene glycol to prepare multiple products |
| CN104163914B (en) * | 2014-07-21 | 2016-05-11 | 金晖兆隆高新科技有限公司 | Utilize maleic anhydride and butanediol to prepare the equipment of voluminous thing |
| CN116120532A (en) * | 2022-12-28 | 2023-05-16 | 常州瑞华化工工程技术股份有限公司 | Preparation method of poly (butylene succinate) and poly (butylene succinate) |
| CN116120532B (en) * | 2022-12-28 | 2024-04-02 | 常州瑞华化工工程技术股份有限公司 | Preparation method of poly (butylene succinate) and poly (butylene succinate) |
| CN116836525A (en) * | 2023-08-09 | 2023-10-03 | 东莞市泰彩色料有限公司 | Environment-friendly degradable color master batch and preparation method thereof |
| CN116836525B (en) * | 2023-08-09 | 2024-02-06 | 东莞市泰彩色料有限公司 | Environment-friendly degradable color master batch and preparation method thereof |
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