CN102718950B - Preparation method of biodegradable polybutylene succinate - Google Patents
Preparation method of biodegradable polybutylene succinate Download PDFInfo
- Publication number
- CN102718950B CN102718950B CN 201210237720 CN201210237720A CN102718950B CN 102718950 B CN102718950 B CN 102718950B CN 201210237720 CN201210237720 CN 201210237720 CN 201210237720 A CN201210237720 A CN 201210237720A CN 102718950 B CN102718950 B CN 102718950B
- Authority
- CN
- China
- Prior art keywords
- succinate
- acetate
- reaction
- compounds
- consumption
- 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
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a preparation method of biodegradable polybutylene succinate (PBS). The preparation method of the biodegradable polybutylene succinate takes a succinate compound and 1, 4-butanediol as polymerizing monomers, adopts an efficient compound catalyst system and comprises the following steps: performing transesterification reaction to obtain a PBS (polybutylene succinate) oligomer first and then performing melting polycondensation reaction to obtain a PBS polymer with a high molecular weight and good color and luster. By the preparation method, PBS degradable plastic with excellent color and luster and a high molecular weight can be prepared without using a chain extender, and meanwhile industrial production can be realized.
Description
Technical field
The invention belongs to the technical field of the standby biodegradable aliphatic polyester of condensation polymerization legal system, be particularly related to a kind of with succinate compounds and 1, the 4-butyleneglycol is polymerization single polymerization monomer, adopt the high efficiency composition catalyst system, prepare the method for high molecular and the good biodegradable poly butylene succinate (PBS) (PBS) of product color by transesterify and polycondensation two-stage process route.
Background technology
In biodegradable aliphatic polyester, poly butylene succinate (PBS) has excellent over-all properties and biodegradability, can compare favourably with traditional polyolefine material, to be hopeful one of material substituted in the conventional polyolefins plastics most, but PBS compares with polyolefin plastics, also there are a certain distance and problem, as low as molecular weight and product color is poor etc., these have all seriously restricted PBS degradative plastics range of application more widely, particularly film field.Based on above reason, people are carrying out a large amount of research work aspect the molecular weight that improves PBS and product color.
CN1424339 has announced a kind of method of the PBS of preparation degradative plastics, the method is with succinic acid and 1, the 4-butyleneglycol is polymerization single polymerization monomer, adopt melt-polycondensation to prepare weight-average molecular weight and reach 100,000, there is the PBS degradative plastics of good physical mechanical property, but do not relate to the aspects such as product color of PBS.CN101328261 has announced a kind of preparation method of high molecular weight PBS degradative plastics, the method is also with succinic acid and 1, the 4-butyleneglycol is polymerization single polymerization monomer, introduces a kind of effective catalyst system, adopts melt-polycondensation to prepare the PBS degradative plastics of weight-average molecular weight between 5-10 ten thousand.But the molecular weight of the PBS degradative plastics prepared by the method is lower, there is no actual application value.CN101077905 has announced a kind of method for preparing the PBS degradative plastics of high molecular, it is prepolymer that the method be take both-end hydroxyl poly-succinic acid-butanediol, then carry out chain extending reaction with the chainextender vulcabond, can obtain weight-average molecular weight and surpass 100,000 PBS degradative plastics, but the method is due to the chainextender that has used isocyanates, there is toxicity, limited the range of application in the food product pack field.
With direct esterification, compare, take succinate compounds and BDO as polymerization single polymerization monomer, adopt the direct melt polycondensation operational path to prepare the PBS degradative plastics, can successfully avoid take succinic acid and BDO and prepare the problem that the PBS degradative plastics exists as monomer.As low as esterification reaction rate, succinic acid reaction not exclusively and the BDO cyclisation generate the problems such as the tetrahydrofuran (THF) side reaction is serious, in addition, in polycondensation phase, can successfully avoid the side reactions such as decarboxylation and cyclisation.The solution of above problem can contribute to improve the molecular weight of PBS and improve product appearance.What is more important, by the method, the content of carboxyl end group of synthetic PBS is extremely low or do not have, and with direct esterification, compares, and can improve to a certain extent appearance luster and the thermostability of PBS degradative plastics.
CN101935391 has announced a kind of preparation method of high-molecular aliphatic polyester, the method be take aliphatic diacid diester and aliphatic diol and is carried out melt phase polycondensation as raw material, can obtain weight-average molecular weight is 5-25 ten thousand, the aliphatic polyester that the molecular weight distribution coefficient is 1.9-2.2, but the shortcoming of the method is that long reaction time and catalyst activity are low, transesterify stage 1 particularly, it is serious that the cyclisation of 4-butyleneglycol generates the side reaction of tetrahydrofuran (THF), this molecular weight that all can have a strong impact on aliphatic polyester further improves and causes raw-material significant wastage, the particularly recovery of by product and processing, can indirectly increase production cost.In addition, the method does not relate to the problems such as product color, and this can seriously limit this product range of application more widely, as the film field.
Summary of the invention
For deficiency of the prior art, the invention discloses the preparation method of a kind of biodegradable poly butylene succinate (PBS) (PBS), the method is with succinate compounds and 1, the 4-butyleneglycol is polymerization single polymerization monomer, adopt the high efficiency composition catalyst system, by transesterify and polycondensation two-stage process route, prepare the PBS degradative plastics.Use that the inventive method can effectively solve that the side reaction existed in the existing technique of PBS is many, molecular weight product is low, the problems such as product color and poor heat stability.
Therefore, one object of the present invention is to provide the preparation method of the PBS degradative plastics of the excellent and high molecular of a kind of product color.But another object of the present invention is to provide a kind of industrialization and without the preparation method of the synthetic PBS degradative plastics of chain extending reaction.
Technical scheme
In order to realize described purpose, the invention provides the preparation method of a kind of biodegradable PBS, it comprises: with succinate compounds and 1, the 4-butyleneglycol is polymerization single polymerization monomer, adopt efficient polycondensation catalyst system, at first, by transesterification reaction, obtain PBS oligopolymer or oligopolymer, then, obtain high molecular and the good PBS superpolymer of product color by melt polycondensation reaction.Specifically comprise following reactions steps:
Transesterification reaction, the succinate compounds monomer weight of take is benchmark, by the succinate compounds, 1, 4-butyleneglycol and transesterification catalyst for example join, in the reactor (there-necked flask) of protection of inert gas, wherein, described succinate compounds and 1, the mol ratio of 4-butyleneglycol is 1:1-1:3, preferred 1:1-1:2, then arrive 150-240 ℃ with temperature-programmed mode temperature reaction system, be warmed up to 160-240 ℃ with temperature-programmed mode again after reaction 10-30min, keep this thermotonus 80-180min to carry out the normal pressure transesterification reaction, until reaching the 95wt% of theoretical liquid outlet quantity, the by product liquid outlet quantity can think that transesterification reaction finishes, with
Polycondensation, the reaction system that to carry out after transesterification reaction cools to 150-160 ℃, connect vacuum system, be evacuated between absolute pressure 1000-50000Pa, preferably, between 5000-20000Pa, reaction 15-30min, remove monomer and the small molecule by-product of not participating in reaction in reaction system, stop vacuumizing and passing into nitrogen, add polycondensation catalyst, thermo-stabilizer and auxiliary agent; Stir 10-30min and guarantee that catalyzer, thermo-stabilizer and auxiliary agent are dispersed in reaction system, stop logical nitrogen, be evacuated to below absolute pressure 100Pa, and be warming up to 200 ℃-240 ℃ of temperature of reaction, keep rapid stirring, under vacuum state, isothermal reaction 60-240min obtains product simultaneously.
In aforesaid method, described succinate compounds is the succinate compounds produced by the whole bag of tricks, is preferably and is selected from one or more in dimethyl succinate, monomethyl succinate, diethyl succinate, single-ethyl succinate, dipropyl succinate and succinic acid list propyl ester.
Described transesterification catalyst is preferably and is selected from one or more in acetate, titanium compound, antimony compounds, germanium compound, tin compound and rare earth compound, and described polycondensation catalyst is preferably and is selected from one or more in titanium compound, antimony compounds, germanium compound, tin compound and rare earth compound.
Preferably, described acetate is to be selected from one or more in Cobaltous diacetate, manganese acetate, magnesium acetate, calcium acetate, zinc acetate, sodium-acetate, plumbic acetate, Burow Solution, cadmium acetate, antimony acetate and Lithium Acetate; Described titanium compound is to be selected from one or more in mixture, titanium dioxide, tetrabutyl titanate, isopropyl titanate, the different monooctyl ester of metatitanic acid four, titanium potassium oxalate(T.P.O.), titanium ethylene glycolate and the butyleneglycol titanium of the titanium dioxide of titanium/silicon mol ratio between 9:1-1:9 and silicon-dioxide; Described antimony compounds is to be selected from one or more in antimonous oxide, antimony acetate and antimony glycol; Described germanium compound is to be selected from one or more in germanium dioxide and germanium chloride; Described tin compound is to be selected from one or more in stannous octoate, stannous oxalate, butyl stannonic acid, Mono-n-butyltin and dibutyl-diethyl octanoate; Described rare earth compound is to be selected from one or more in Lanthanum trichloride, hafnium chloride, rubidium chloride, Yttrium trichloride, methyl ethyl diketone lanthanum, methyl ethyl diketone hafnium, methyl ethyl diketone rubidium and methyl ethyl diketone yttrium.
More preferably, described polycondensation catalyst is to be selected from one or more in mixture, tetrabutyl titanate, isopropyl titanate, titanium dioxide, antimonous oxide, antimony acetate, antimony glycol, germanium dioxide, germanium chloride, stannous octoate, stannous oxalate, Lanthanum trichloride, hafnium chloride, methyl ethyl diketone lanthanum, methyl ethyl diketone hafnium, sodium-acetate, calcium acetate, magnesium acetate, Burow Solution and the Lithium Acetate of the titanium dioxide of titanium/silicon mol ratio between 9:1-1:9 and silicon-dioxide.
Described thermo-stabilizer is preferably phosphoric acid or phosphorons acid compound, and described auxiliary agent is preferably and is selected from lubricant, nucleator and C
3-C
12the aliphatics trivalent alcohol in one or more.
More preferably, described thermo-stabilizer is to be selected from one or more in phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate, trimethyl phosphite 99, triethyl phosphate, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite and diphenyl phosphite; Described lubricant is to be selected from one or more in stearic acid, stearate, paraffin and stearic amide; Described nucleator is to be selected from one or more in talcum, titanium dioxide, silicon-dioxide, mica, polynite and organic carboxylate; The aliphatics trivalent alcohol of described C3-C12 is to be selected from one or more in BT and Glycerin.
The consumption of described transesterification catalyst is preferably the 0.01-5wt% of succinate compounds, more preferably 0.01-1wt%, most preferably 0.1-0.5wt%; The consumption of described polycondensation catalyst is preferably the 0.01-5wt% of succinate compounds, more preferably 0.01-1wt%, most preferably 0.1-1wt%; The consumption of described thermo-stabilizer is preferably the 0.001-5wt% of succinate compounds, more preferably 0.001-1wt%, most preferably 0.01-0.5wt%; The consumption of described auxiliary agent is preferably the 0.001-1wt% of succinate compounds, more preferably 0.001-0.5wt%, most preferably 0.05-0.5wt%.
In aforesaid method, the speed of intensification and cooling all is preferably set to 5-10 ℃/min.
Beneficial effect
It is polymerization single polymerization monomer that succinate compounds and BDO are take in the present invention, adopts the high efficiency composition catalyst system, prepares the method for high molecular and the good biodegradable PBS degradative plastics of product color by transesterify and polycondensation two-stage process route.Mainly contain following advantage:
1. with succinic acid and 1, the 4-butyleneglycol is that monomer prepares the PBS processing method and compares, utilize processing method disclosed by the invention, can effectively solve or avoid in existing Technology to have in Esterification Stage that esterification reaction rate is low, the succinic acid reaction not thoroughly, the BDO cyclisation produces the problem that the side reactions such as decarboxylation and cyclisation easily occur the high and polycondensation phase of Tetrahydrofuran growing amount.And the solution of the problems referred to above will contribute to improve molecular weight and the product appearance color and luster of PBS degradative plastics;
2. with take succinic acid and compare as monomer prepares the PBS processing method with BDO, utilize processing method disclosed by the invention, by-product carbinol, ethanol and propyl alcohol can reclaim and reuse by condensation, have to reduce pollute and be conducive to the advantage such as environmental protection.In addition, this processing method also has by product less and the product yield advantages of higher;
3. with succinate and 1, the 4-butyleneglycol is that monomer prepares the PBS processing method and compares, it is few that the polymerization process condition that the present invention announces has a by product, particularly, in the transesterify stage, the content that the BDO cyclisation generates Tetrahydrofuran is very low, be less than 0.5%(and in ordinary method the Tetrahydrofuran turnout be greater than 10%), the recovery utilization rate that this contributes to improve BDO, reduce production costs indirectly;
4. with succinate and 1, the 4-butyleneglycol is that monomer prepares the PBS processing method and compares, the polymerization process condition that the present invention announces and complex catalyst system significantly shorten polymerization time, and (wherein, weight-average molecular weight is greater than 100,000 to obtain high molecular and coloury PBS degradative plastics; The b value is less than 5); Simultaneously, owing to not using chainextender, can further enlarge the range of application of PBS degradative plastics in the food product pack field.
Embodiment
Below provide embodiment; but it is to be noted that the present invention is not limited to these and implements example; some nonessential change and adjustment that the ordinary skill of this area is made the present invention according to the content of described invention, still belong to protection scope of the present invention.
Except specified otherwise, equipment used of the present invention and method are the general equipment in this area and method.1515-2414 type gel permeation chromatography (GPC) instrument of the molecular weight and molecualr weight distribution coefficients by using U.S. Waters company of PBS degradative plastics is measured, trichloromethane is moving phase, take-off rate is 1ml/min, and column temperature is 30 ° of C, and standard is polystyrene.The form and aspect of PBS (L value and b value) adopt the automatic color difference meter of the Color35 of BYKGardner company type automatically to be measured.PBS transesterify and polycondensation phase Analysis of By-product adopt the 7890A of Anjelen Sci. & Tech. Inc type gas chromatograph to analyze.
Embodiment 1
Take respectively dimethyl succinate 58.4g, BDO 43.2g, manganese acetate 0.01g, zinc acetate 0.01g join in the 250ml there-necked flask, wherein connect flatly stirring, connect flatly nitrogen protection, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; The temperature-programmed mode (temperature rise rate is 5 ℃/min) of take after reaction 10min is warmed up to 175 ℃; Keep this thermotonus 120min and think that transesterification reaction finishes until the methyl alcohol liquid outlet quantity reaches the 95wt% of theoretical value.By product is mainly main by methyl alcohol and tetrahydrofuran (THF), and wherein, content of tetrahydrofuran is 0.1%.In addition, also have a small amount of unreacted dimethyl succinate and BDO.After transesterification reaction finishes, system is lowered the temperature to (10 ℃/min of cooling rate) to 155 ℃, remove water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and start to be evacuated to absolute pressure 10000Pa, reaction 30min, do not participate in monomer and the by product reacted in the removal system.Stop vacuumizing and passing into nitrogen, add the mixture 0.20g (wherein, antimonous oxide 0.15g, methyl ethyl diketone lanthanum 0.05g) of antimonous oxide and methyl ethyl diketone lanthanum, triphenyl phosphite 0.01g, BT 0.25g; Stir 10min and guarantee that catalyzer and auxiliary agent are dispersed in reaction system.Stop logical nitrogen, be evacuated to below absolute pressure 100Pa, and be rapidly heated (temperature rise rate is 5 ℃/min) is to 230 ℃, keep rapid stirring simultaneously, isothermal reaction 100min under vacuum state is until product viscosity increases and pole-climbing, and (the polycondensation phase by product is comprised of BDO and PBS oligopolymer to obtain product, the content of BDO is 81%).Then product being carried out to compression molding carries out the form and aspect test or it is dissolved in to chloroform then with carrying out the molecular weight and molecualr weight distribution test after methanol extraction.
The weight-average molecular weight of measuring product is 129300g/mol, and the molecular weight distribution coefficient is 1.9, and colourity b value is 0.4.
Embodiment 2
Take respectively monomethyl succinate 58.4g, BDO 50.4g isopropyl titanate 0.02g and magnesium acetate 0.02g and join in the 250ml there-necked flask, wherein connect flatly stirring, connect flatly nitrogen protection, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 160 ℃; The temperature-programmed mode (temperature rise rate is 5 ℃/min) of take after reaction 20min is warmed up to 185 ℃; Keep this thermotonus 120min and think that reaction finishes until by-product carbinol and water liquid outlet quantity reach the 95wt% of theoretical value.By product is mainly main by methyl alcohol, water and tetrahydrofuran (THF), and wherein, content of tetrahydrofuran is 0.2%.In addition, also have a small amount of unreacted monomethyl succinate and BDO.System is lowered the temperature to (10 ℃/min of cooling rate) to 155 ℃, remove water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and start to be evacuated to absolute pressure 5000Pa left and right, reaction 15min, do not participate in monomer and the by product reacted in the removal system.Stop vacuumizing and passing into nitrogen, add the about 0.20g(of mixture of the mixture of titanium dioxide that titanium/silicon mol ratio is 9:1 and silicon-dioxide and antimonous oxide wherein, the mixture 0.05g of the titanium dioxide that titanium/silicon mol ratio is 9:1 and silicon-dioxide, antimonous oxide 0.15g), triphenyl phosphite 0.02g, calcium stearate 0.05g; Stir 15min and guarantee that catalyzer, thermo-stabilizer and auxiliary agent are dispersed in reaction system.Stop logical nitrogen, be evacuated to below absolute pressure 100Pa, and be rapidly heated (temperature rise rate is 5 ℃/min) is to 230 ℃, keep rapid stirring simultaneously, isothermal reaction 120min under vacuum state is until product viscosity increases and pole-climbing, and (the polycondensation phase by product is comprised of BDO and PBS oligopolymer to obtain product, the content of BDO is 75%).Then product being carried out to compression molding carries out the form and aspect test or it is dissolved in to chloroform then with carrying out the molecular weight and molecualr weight distribution test after methanol extraction.
The weight-average molecular weight of measuring product is 138400g/mol, and the molecular weight distribution coefficient is 2.0, and colourity b value is 0.6.
Embodiment 3
Take respectively dimethyl succinate 58.4g, BDO 43.2g, isopropyl titanate 0.01g and calcium acetate 0.02g and join in the 250ml there-necked flask, wherein connect flatly stirring, connect flatly nitrogen protection, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Temperature programming (temperature rise rate the is 5 ℃/min) mode of take after reaction 10min is warmed up to 200 ℃; Keep this thermotonus 80min and think that transesterification reaction finishes until the methyl alcohol liquid outlet quantity reaches the 95wt% of theoretical value.By product is mainly main by methyl alcohol and tetrahydrofuran (THF), and wherein, content of tetrahydrofuran is 0.15%.In addition, also have a small amount of unreacted dimethyl succinate and BDO.After transesterification reaction finishes, system is lowered the temperature to (10 ℃/min of cooling rate) to 155 ℃, remove water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and start to be evacuated to below absolute pressure 10000Pa, reaction 15min, do not participate in monomer and the by product reacted in the removal system.Stop vacuumizing and passing into nitrogen, add germanium dioxide 0.30g, triethyl phosphate 0.03g, calcium stearate 0.05g; Stir 10min and guarantee that catalyzer, thermo-stabilizer and auxiliary agent are dispersed in reaction system.Stop logical nitrogen, be evacuated to below absolute pressure 50Pa, and be rapidly heated (temperature rise rate is 5 ℃/min) is to 230 ℃, keep rapid stirring simultaneously, isothermal reaction 180min under vacuum state is until product viscosity increases and pole-climbing, and (the polycondensation phase by product is comprised of BDO and PBS oligopolymer to obtain product, the content of BDO is 77%).Then product being carried out to compression molding carries out the form and aspect test or it is dissolved in to chloroform then with carrying out the molecular weight and molecualr weight distribution test after methanol extraction.
The weight-average molecular weight of measuring product is 117300g/mol, and the molecular weight distribution coefficient is 1.8, and colourity b value is 0.5.
Embodiment 4
Take respectively diethyl succinate 69.9g, BDO 39.6g, calcium acetate 0.01g, manganese acetate 0.01g and titanium dioxide 0.02g and join in the 250ml there-necked flask, wherein connect flatly stirring, connect flatly nitrogen protection, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Temperature programming (temperature rise rate the is 5 ℃/min) mode of take after reaction 10min is warmed up to 200 ℃; Keep this thermotonus 90min) until reaching the 95wt% of theoretical value, the ethanol liquid outlet quantity thinks that reaction finishes.By product is mainly main by ethanol and tetrahydrofuran (THF), and wherein, content of tetrahydrofuran is 0.1%.In addition, also have a small amount of unreacted diethyl succinate and BDO.System is lowered the temperature to (10 ℃/min of cooling rate) to 155 ℃, remove water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and start to be evacuated to absolute pressure 5000Pa, reaction 15min, do not participate in monomer and the by product reacted in the removal system.Stop vacuumizing and passing into nitrogen, add titanium dioxide that titanium/silicon mol ratio is 6:4 and the mixture 0.10g of silicon-dioxide, triphenyl phosphite 0.01g, calcium stearate 0.05g; Stir 10min and guarantee that catalyzer and auxiliary agent are dispersed in reaction system.Stop logical nitrogen, be evacuated to below absolute pressure 50Pa, and be rapidly heated (temperature rise rate is 5 ℃/min) is to 230 ℃, keep rapid stirring simultaneously, isothermal reaction 100min under vacuum state is until product viscosity increases and pole-climbing, and (the polycondensation phase by product is comprised of BDO and PBS oligopolymer to obtain product, the content of BDO is 74%).Then product being carried out to compression molding carries out the form and aspect test or it is dissolved in to chloroform then with carrying out the molecular weight and molecualr weight distribution test after methanol extraction.
The weight-average molecular weight of measuring product is 159400g/mol, and the molecular weight distribution coefficient is 2.3, and colourity b value is 1.6.
Embodiment 5
Take respectively dimethyl succinate 58.4g, BDO 43.2g, zinc acetate 0.03g and calcium acetate 0.01g and join in the 250ml there-necked flask, wherein connect flatly stirring, connect flatly nitrogen protection, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; Temperature programming (temperature rise rate the is 5 ℃/min) mode of take after reaction 10min is warmed up to 180 ℃; Keep this thermotonus 150min and think that transesterification reaction finishes until the methyl alcohol liquid outlet quantity reaches the 95wt% of theoretical value.By product is mainly main by methyl alcohol and tetrahydrofuran (THF), and wherein, content of tetrahydrofuran is 0.1%.In addition, also have a small amount of unreacted dimethyl succinate and BDO.After transesterification reaction finishes, system is lowered the temperature to (10 ℃/min of cooling rate) to 150 ℃, remove water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and start to be evacuated to below absolute pressure 10000Pa, reaction 15min, do not participate in monomer and the by product reacted in the removal system.Stop vacuumizing and passing into nitrogen, add mixture 0.30g(that polycondensation catalyst system antimonous oxide and titanium/silicon mol ratio are titanium dioxide between 1:4 and silicon-dioxide wherein, antimonous oxide 0.25g, the mixture 0.05g of titanium dioxide and silicon-dioxide), thermo-stabilizer triphenyl phosphite 0.03g, lubricant stearic acid calcium 0.05g, auxiliary agent 1,2,3-glycerol 0.20g; Stir 10min and guarantee that catalyzer, thermo-stabilizer and auxiliary agent are dispersed in reaction system.Stop logical nitrogen, be evacuated to below absolute pressure 50Pa, and be rapidly heated (temperature rise rate is 5 ℃/min) is to 230 ℃, keep rapid stirring simultaneously, isothermal reaction 90min under vacuum state is until product viscosity increases and pole-climbing, and (the polycondensation phase by product is comprised of BDO and PBS oligopolymer to obtain product, the content of BDO is 74%).Then product being carried out to compression molding carries out the form and aspect test or it is dissolved in to chloroform then with carrying out the molecular weight and molecualr weight distribution test after methanol extraction.
The weight-average molecular weight of measuring product is 105500g/mol, and the molecular weight distribution coefficient is 2.2, and colourity b value is 0.9.
Embodiment 6
Take respectively single-ethyl succinate 58.5g, 1,4-butyleneglycol 39.6g isopropyl titanate 0.01g, zinc acetate 0.01g, calcium acetate 0.01g and magnesium acetate 0.01g join in the 250ml there-necked flask, wherein connect flatly stirring, connect flatly nitrogen protection, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 150 ℃; The temperature-programmed mode (temperature rise rate is 5 ℃/min) of take after reaction 20min is warmed up to 180 ℃; Keep this thermotonus 120min and think that reaction finishes until liquid outlet quantity reaches the 95wt% of theoretical value.By product is mainly main by ethanol, water and tetrahydrofuran (THF), and wherein, content of tetrahydrofuran is 0.1%.In addition, also have a small amount of unreacted single-ethyl succinate and BDO.System is lowered the temperature to (10 ℃/min of cooling rate) to 150 ℃, remove water trap and prolong when continuing logical nitrogen, connect the vacuum pump interface, close the channel of nitrogen valve and start to be evacuated to absolute pressure 20000Pa left and right, reaction 30min, do not participate in monomer and the by product reacted in the removal system.Stop vacuumizing and passing into nitrogen, add the about 0.25g(of mixture of the mixture of titanium dioxide that titanium/silicon mol ratio is 7:3 and silicon-dioxide and antimonous oxide wherein, the mixture 0.05g of titanium dioxide and silicon-dioxide, antimonous oxide 0.20g), triphenyl phosphite 0.02g, calcium stearate 0.05g, Glycerin 0.20g; Stir 15min and guarantee that catalyzer, thermo-stabilizer and auxiliary agent are dispersed in reaction system.Stop logical nitrogen, be evacuated to below absolute pressure 50Pa, and be rapidly heated (temperature rise rate is 5 ℃/min) is to 230 ℃, keep rapid stirring simultaneously, isothermal reaction 110min under vacuum state is until product viscosity increases and pole-climbing, and (the polycondensation phase by product is comprised of BDO and PBS oligopolymer to obtain product, the content of BDO is 79%).Then product being carried out to compression molding carries out the form and aspect test or it is dissolved in to chloroform then with carrying out the molecular weight and molecualr weight distribution test after methanol extraction.
The weight-average molecular weight of measuring product is 145500g/mol, and the molecular weight distribution coefficient is 2.2, and colourity b value is 1.1.
Comparative example 1
Take respectively dimethyl succinate 58.4g, BDO 43.2g, tosic acid 0.02g, titanic acid ester 0.08g join in the 250ml there-necked flask, wherein connect flatly stirring, connect flatly nitrogen protection, another mouth connects water trap and distillation column; Start stirring, reacting by heating system to 180 ℃; Keep this thermotonus 180min and can think that transesterification reaction finishes until the liquid outlet quantity of methyl alcohol reaches the 95wt% of theoretical value.By product is mainly main by methyl alcohol and tetrahydrofuran (THF), and wherein, content of tetrahydrofuran is 15%.In addition, also have a small amount of unreacted dimethyl succinate and BDO.After transesterification reaction finishes, add titanic acid ester 0.1g and tosic acid 0.1g, and be rapidly heated to 230 ℃, keep rapid stirring simultaneously, control vacuum tightness absolute pressure 30Pa, under vacuum state, isothermal reaction 250min obtains product (the polycondensation phase by product is comprised of BDO, tetrahydrofuran (THF) and PBS oligopolymer, wherein, 1, the content of 4-butyleneglycol is 55%, and content of tetrahydrofuran is that 20%, PBS oligopolymer is 25%).Then product being carried out to compression molding carries out the form and aspect test or it is dissolved in to chloroform then with carrying out the molecular weight and molecualr weight distribution test after methanol extraction.
The weight-average molecular weight of measuring product is 104500g/mol, and the molecular weight distribution coefficient is 1.9, and colourity b value is 8.5.
Claims (10)
1. the preparation method of a biodegradable poly butylene succinate (PBS), it comprises following reactions steps:
Transesterification reaction, the succinate compounds monomer weight of take is benchmark, by the succinate compounds, 1, 4-butyleneglycol and transesterification catalyst join in the reactor of protection of inert gas, wherein, described succinate compounds and 1, the mol ratio of 4-butyleneglycol is 1:1-1:3, then arrive 150-240 ℃ with temperature-programmed mode temperature reaction system, be warmed up to 160-240 ℃ with temperature-programmed mode again after reaction 10-30min, keep this thermotonus 80-180min to carry out the normal pressure transesterification reaction, until reaching the 95wt% of theoretical liquid outlet quantity, the by product liquid outlet quantity thinks that transesterification reaction finishes, with
Polycondensation, the reaction system that to carry out after transesterification reaction cools to 150-160 ℃, connect vacuum system, be evacuated between absolute pressure 1000-50000Pa, reaction 15-30min, remove monomer and the small molecule by-product of not participating in reaction in reaction system, stop vacuumizing and passing into nitrogen, add polycondensation catalyst, thermo-stabilizer and auxiliary agent, stir 10-30min and guarantee catalyzer, thermo-stabilizer and auxiliary agent are dispersed in reaction system, stop logical nitrogen, be evacuated to below absolute pressure 100Pa, and be warming up to 200 ℃-240 ℃ of temperature of reaction, keep rapid stirring simultaneously, under vacuum state, isothermal reaction 60-240min obtains product,
Wherein, described transesterification catalyst is to be selected from one or more in acetate, titanium compound, antimony compounds, germanium compound, tin compound and rare earth compound, and described polycondensation catalyst is to be selected from one or more in titanium compound, antimony compounds, germanium compound, tin compound and rare earth compound;
Described thermo-stabilizer is phosphoric acid or phosphorons acid compound, and described auxiliary agent is for being selected from lubricant, nucleator and C
3-C
12the aliphatics trivalent alcohol in one or more.
2. method according to claim 1, wherein, the mol ratio of described succinate compounds and BDO is 1:1-1:2.
3. method according to claim 2, wherein, described succinate compounds is to be selected from one or more in dimethyl succinate, monomethyl succinate, diethyl succinate, single-ethyl succinate, dipropyl succinate and succinic acid list propyl ester.
4. method according to claim 1, wherein, described acetate is to be selected from one or more in Cobaltous diacetate, manganese acetate, magnesium acetate, calcium acetate, zinc acetate, sodium-acetate, plumbic acetate, Burow Solution, cadmium acetate, antimony acetate and Lithium Acetate; Described titanium compound is to be selected from one or more in mixture, titanium dioxide, tetrabutyl titanate, isopropyl titanate, the different monooctyl ester of metatitanic acid four, titanium potassium oxalate(T.P.O.), titanium ethylene glycolate and the butyleneglycol titanium of the titanium dioxide of titanium/silicon mol ratio between 9:1-1:9 and silicon-dioxide; Described antimony compounds is to be selected from one or more in antimonous oxide, antimony acetate and antimony glycol; Described germanium compound is to be selected from one or more in germanium dioxide and germanium chloride; Described tin compound is to be selected from one or more in stannous octoate, stannous oxalate, butyl stannonic acid, Mono-n-butyltin and dibutyl-diethyl octanoate; Described rare earth compound is to be selected from one or more in Lanthanum trichloride, hafnium chloride, rubidium chloride, Yttrium trichloride, methyl ethyl diketone lanthanum, methyl ethyl diketone hafnium, methyl ethyl diketone rubidium and methyl ethyl diketone yttrium.
5. method according to claim 4, wherein, described polycondensation catalyst is to be selected from one or more in mixture, tetrabutyl titanate, isopropyl titanate, titanium dioxide, antimonous oxide, antimony acetate, antimony glycol, germanium dioxide, germanium chloride, stannous octoate, stannous oxalate, Lanthanum trichloride, hafnium chloride, methyl ethyl diketone lanthanum, methyl ethyl diketone hafnium, sodium-acetate, Cobaltous diacetate, calcium acetate, magnesium acetate, Burow Solution and the Lithium Acetate of the titanium dioxide of titanium/silicon mol ratio between 9:1-1:9 and silicon-dioxide.
6. method according to claim 1, wherein, described thermo-stabilizer is to be selected from one or more in phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate, trimethyl phosphite 99, triethyl phosphate, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triphenyl phosphite and diphenyl phosphite; Described lubricant is to be selected from one or more in stearic acid, stearate, paraffin and stearic amide; Described nucleator is to be selected from one or more in talcum, titanium dioxide, silicon-dioxide, mica, polynite and organic carboxylate; Described C
3-C
12the aliphatics trivalent alcohol be to be selected from one or more in BT and Glycerin.
7. according to the described method of one of claims 1 to 3, wherein, the 0.01-5wt% that the consumption of described transesterification catalyst is the succinate compounds; The 0.01-5wt% that the consumption of described polycondensation catalyst is the succinate compounds; The 0.001-5wt% that the consumption of described thermo-stabilizer is the succinate compounds; The 0.001-1wt% that the consumption of described auxiliary agent is the succinate compounds.
8. method according to claim 7, wherein, the 0.01-1wt% that the consumption of described transesterification catalyst is the succinate compounds; The 0.01-1wt% that the consumption of described polycondensation catalyst is the succinate compounds; The 0.001-1wt% that the consumption of described thermo-stabilizer is the succinate compounds; The 0.001-0.5wt% that the consumption of described auxiliary agent is the succinate compounds.
9. method according to claim 8, wherein, the 0.1-0.5wt% that the consumption of described transesterification catalyst is the succinate compounds; The 0.1-1wt% that the consumption of described polycondensation catalyst is the succinate compounds; The 0.01-0.5wt% that the consumption of described thermo-stabilizer is the succinate compounds; The 0.05-0.5wt% that the consumption of described auxiliary agent is the succinate compounds.
10. according to the described method of one of claims 1 to 3, wherein, the speed of intensification and cooling all is set as 5-10 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210237720 CN102718950B (en) | 2012-07-09 | 2012-07-09 | Preparation method of biodegradable polybutylene succinate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210237720 CN102718950B (en) | 2012-07-09 | 2012-07-09 | Preparation method of biodegradable polybutylene succinate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102718950A CN102718950A (en) | 2012-10-10 |
| CN102718950B true CN102718950B (en) | 2013-12-25 |
Family
ID=46944835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210237720 Active CN102718950B (en) | 2012-07-09 | 2012-07-09 | Preparation method of biodegradable polybutylene succinate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102718950B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122056B (en) * | 2013-01-21 | 2016-03-23 | 安徽雪郎生物科技股份有限公司 | A kind of biodegradable poly-succinic fumaric acid butanediol ester and preparation method thereof |
| CN105418900B (en) * | 2016-01-12 | 2017-07-28 | 中国科学院长春应用化学研究所 | The preparation method of poly butylene succinate and polylactic-acid block copolymer |
| CN112694602B (en) * | 2020-12-24 | 2022-05-27 | 宁波窦氏化学科技有限公司 | Method for preparing biodegradable plastic PBS |
| CN113896868B (en) * | 2021-09-28 | 2023-04-07 | 天津工业大学 | Method for preparing polybutylene succinate by taking dimethyl succinate as raw material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332996C (en) * | 2004-12-22 | 2007-08-22 | 中国科学院化学研究所 | Modified butanediol ester poly succinic acid and synthetic method |
-
2012
- 2012-07-09 CN CN 201210237720 patent/CN102718950B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102718950A (en) | 2012-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102746493B (en) | Preparation method of all-biological-base poly butylenes succinate (PBS) | |
| CN102718949B (en) | Preparation method of polybutylene succinate | |
| CN102718950B (en) | Preparation method of biodegradable polybutylene succinate | |
| US8933162B2 (en) | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof | |
| US20180186930A1 (en) | Use of additives to fine-tune the composition of carbonate units in a polymer formed by copolymerization of co2 with epoxide: application to the synthesis of polycarbonate-based block copolymers and of telechelics | |
| CN102585286B (en) | Method for regenerating polyol by using waste polyurethane | |
| KR101409431B1 (en) | Polyester polymer having excellent transparency and method for producing the same | |
| CN102174176A (en) | Preparation method of thermosetting type pure polyester resin capable of resisting high-temperature yellowing | |
| CN104418997A (en) | Synthetic method of polyethylene glycol terephthalate from biomass glycol | |
| CN107955142B (en) | Process for preparing isosorbide-containing polyesters | |
| US20190315915A1 (en) | New high molecular weight polymers from waste raw materials | |
| CN114891189B (en) | Preparation method of low-chroma PETG copolyester | |
| TW201422662A (en) | Continuous preparation method of biodegradable aliphatic/aromatic polyester copolymer | |
| CN102731752B (en) | Preparation method of fully biobased polybuthylenesuccinate | |
| CN102718948B (en) | Method for preparing aliphatic polyoxalate | |
| CN114533646A (en) | Anti-wrinkle repair moisturizing essence containing ectoine and preparation method thereof | |
| CN103396537A (en) | Preparation method of high temperature yellowing resistant thermosetting polyester resin | |
| CN104031246B (en) | The preparation method of full biological poly (terephthalic acid (TPA) butanediol-altogether-adipic acid butanediol) ester of HMW and color and luster excellence | |
| CN113993950A (en) | High-strength ultrathin biodegradable film and preparation method thereof | |
| CN111087592A (en) | Polybutylene terephthalate catalyst and preparation method thereof | |
| CN106715522A (en) | A continuous method for manufacturing a polyester from cyclic ester monomer | |
| CN108707213A (en) | A kind of preparation method of hyper-branched block high-molecular copolymer and application | |
| Wu et al. | Synthesis and characterization of high molecular weight poly (1, 2-propylene carbonate-co-1, 2-cyclohexylene carbonate) using zinc complex catalyst | |
| CN115160553A (en) | Polycarbonate ultraviolet low-temperature curing powder coating and preparation method thereof | |
| Song et al. | Synthesis of polycarbonate diols (PCDLs) via two-step process using CH3COONa as an effective catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20130517 Address after: 100070 Beijing city Fengtai District South Fourth Ring Road No. 188 District No. 21 Applicant after: Xuyang Chemical Technology Research Institute Co., Ltd. Address before: 100070 Beijing city Fengtai District South Fourth Ring Road No. 188 District No. 21 Applicant before: Beijing Xuyang Chemical Technology Research Institute Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CANGZHOU XUYANG CHEMICAL CO., LTD. Free format text: FORMER OWNER: XUYANG CHEMICAL TECHNOLOGY INSTITUTE CO., LTD. Effective date: 20141105 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 100070 FENGTAI, BEIJING TO: 061100 CANGZHOU, HEBEI PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20141105 Address after: 061100 Hebei province Cangzhou city Bohai District South Road on the north side of the port Patentee after: Cangzhou Xu Yang Chemical Co., Ltd. Address before: 100070 Beijing city Fengtai District South Fourth Ring Road No. 188 District No. 21 Patentee before: Xuyang Chemical Technology Research Institute Co., Ltd. |
|
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Yingwei Inventor after: Wang Guoli Inventor after: Chen Xibo Inventor after: Zhang Xinzhi Inventor after: Sun Changjiang Inventor before: Zhang Yingwei Inventor before: Wang Guoli Inventor before: Zhang Xinzhi Inventor before: Sun Changjiang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHANG YINGWEI WANG GUOLI ZHANG XINZHI SUN CHANGJIANG TO: ZHANG YINGWEI WANG GUOLI CHEN XIBO ZHANG XINZHI SUN CHANGJIANG |