CN102718949A - Preparation method of polybutylene succinate - Google Patents
Preparation method of polybutylene succinate Download PDFInfo
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- CN102718949A CN102718949A CN2012102376941A CN201210237694A CN102718949A CN 102718949 A CN102718949 A CN 102718949A CN 2012102376941 A CN2012102376941 A CN 2012102376941A CN 201210237694 A CN201210237694 A CN 201210237694A CN 102718949 A CN102718949 A CN 102718949A
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Abstract
The invention provides a preparation method of polybutylene succinate. The preparation method of the polybutylene succinate takes mono-methyl succinate and 1, 4-butanediol as monomers, adopts an efficient compound catalyst system and comprises the following steps: reacting to obtain a PBS (polybutylene succinate) oligomer first and then performing polycondensation reaction to obtain a PBS polymer with a high molecular weight and good color and luster. Through the adoption of the preparation method, on one hand, the problems that in the conventional technology that succinic acid and the 1, 4-butanediol are taken as monomers to prepare the PBS, the speed rate of esterification reaction is low, the succinic acid cannot react completely, and the amount of a generated byproduct tetrahydrofuran is high can be solved; on the other hand, the acidicity of the mono-methyl succinate is less than that of the succinic acid, so that corrosion to equipment is reduced, and thus the maintenance cost of the equipment is reduced and greater contribution is made to industrial production; in addition, a chain extender is not used, the application range of PBS degradable plastic in the field of food packaging can be further expanded.
Description
Technical field
The present invention relates to the preparation method of a kind of poly butylene succinate (PBS); Be specifically related to a kind of with monomethyl succinate and 1; The 4-butyleneglycol is a polymerization single polymerization monomer, adopts the efficient composite catalyst system, waits the method for preparing poly butylene succinate through esterification and polycondensation.
Background technology
Poly butylene succinate (PBS) is very important a kind of macromolecular material in the aliphatic polyester; Have excellent mechanical property, thermal property and biodegradability; Be fundamentally to solve one of effective way by conventional polyolefins material caused " white pollution " problem, it is widely used in fields such as sheet material, sheet material and film.
Up to the present, in the technology of preparation poly butylene succinate, also do not relate to monomethyl succinate and 1, the 4-butyleneglycol is the public reported that polymerization single polymerization monomer prepares PBS.Reported the method for preparing PBS with aliphatic dibasic acid and divalent alcohol polymerization single polymerization monomer among the U.S. Pat 5310782A, but its molecular weight is about 30000 only, actual application value is little.Among U.S. Pat 5391633, US5348700 and the US5525409 play-by-play adopt to add the method that the chainextender isocyanate compound improves the PBS molecular weight; PBS weight-average molecular weight through the preparation of chain extension method can reach about 170000, but has had a strong impact on the range of application of product in fields such as food product pack owing to the chainextender isocyanate compound has bio-toxicity.Reported a kind of preparation method of high molecular weight PBS among the Chinese patent CN101328261A; Its characteristics adopt the catalystsystem of cerium salt-antimony glycol; Can obtain weight-average molecular weight is 5.6-12.5 ten thousand; Breaking tenacity 35-55MPa, elongation at break are the PBS of 200-420%, but this method exists small molecular by product to reach problems such as product yield is low more.Chinese patent CN1424339A has reported the method for a kind of PBS of preparation, and the PBS weight-average molecular weight through the preparation of this method can reach about 100,000, has the aliphatic polyester of good mechanical properties, but does not relate to the problem of aspect such as product color.Above related patent U.S. Patent No. all is to be raw material with the Succinic Acid, can exist esterification reaction rate low, and the Succinic Acid reaction not exclusively reaches 1, and problems such as by product THF growing amount is big are produced in the cyclisation of 4-butyleneglycol, cause product yield low.In addition, diprotic acid is very high to equipment corrosion, causes problems such as facility investment height, increases the manufacturing cost of product indirectly.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of poly butylene succinate (PBS); Utilize preparation method provided by the invention; Overcome the many and high problem of by product THF turnout of water byproduct content in the prior art on the one hand; The recyclable utilization of methyl alcohol that generates simultaneously, the added value of raising by product; On the other hand, substitute traditional Succinic Acid with monomethyl succinate and prepare PBS, and then effectively overcome the Succinic Acid problem high equipment corrosion.
To achieve these goals, the present invention provides the preparation method of a kind of poly butylene succinate (PBS), and this method is with monomethyl succinate and 1; The 4-butyleneglycol is a monomer; Adopt the efficient composite catalyst system, at first, obtain PBS oligopolymer or oligopolymer through reaction; Then, obtain HMW and coloury PBS superpolymer through polycondensation.Specifically comprise the steps:
Step 1, be benchmark with the monomethyl succinate monomer weight, with monomethyl succinate, 1,4-butyleneglycol and catalysts join in the reactor drum (for example there-necked flask) of protection of inert gas; Wherein, said monomethyl succinate and 1, the mol ratio of 4-butyleneglycol is 1:1-1:3; Preferred 1:1-1:1.6 arrives 150-220 ℃ with temperature-programmed mode temperature reaction system then, keeps this thermotonus 60-300min; Be warmed up to 160-240 ℃ with temperature-programmed mode more afterwards; Keep this thermotonus 80-180min to carry out synthesis under normal pressure, the 90wt% that reaches theoretical liquid outlet quantity up to the by product liquid outlet quantity can think that reaction finishes
Step 2, polycondensation, the reaction system that will carry out behind the synthesis under normal pressure cools to 140-150 ℃, connects vacuum system; Be evacuated between the absolute pressure 1000-50000Pa; Between the preferred 5000-20000Pa, reaction 15-30min removes monomer and the small molecule by-product of not participating in reaction in the reaction system; Stop to vacuumize and feeding nitrogen, add polycondensation catalyst, thermo-stabilizer and auxiliary agent; Stir 10-30min and guarantee that catalyzer, thermo-stabilizer and auxiliary agent are dispersed in the reaction system; Stop logical nitrogen; Be evacuated to below the absolute pressure 100Pa, and be rapidly heated, keep simultaneously stirring fast to 200 ℃-240 ℃ of temperature of reaction; Isothermal reaction 60-240min promptly obtains product under vacuum state
Perhaps, this method comprises the steps:
Step 1, be benchmark with the monomethyl succinate monomer weight, with monomethyl succinate, 1,4-butyleneglycol and catalysts join in the reactor drum (for example there-necked flask) of protection of inert gas; Wherein, said monomethyl succinate and 1, the mol ratio of 4-butyleneglycol is 1:1-1:3; Preferred 1:1-1:1.6; Arrive 150-220 ℃ with temperature-programmed mode temperature reaction system then, keep this thermotonus 10-300min to carry out negative reaction, wherein the vacuum tightness of negative reaction remains between the absolute pressure 5000-20000Pa; Between the preferred 5000-10000Pa, the 90wt% that reaches theoretical liquid outlet quantity up to the by product liquid outlet quantity can think that reaction finishes;
Step 2, polycondensation stop to vacuumize and feeding nitrogen behind the negative reaction, add polycondensation catalyst, thermo-stabilizer and auxiliary agent; Stir 10-30min and guarantee that catalyzer, thermo-stabilizer and auxiliary agent are dispersed in the reaction system; Stop logical nitrogen; Be evacuated to below the absolute pressure 100Pa; And be rapidly heated to 200 ℃-240 ℃ of temperature of reaction, keeping simultaneously stirring fast, isothermal reaction 60-240min promptly obtains product under vacuum state.
In aforesaid method, said monomethyl succinate comprises the monomethyl succinate of producing through the whole bag of tricks.
In aforesaid method, the catalysts in the said step 1 is preferably and is selected from acetate, titanium compound, antimony compounds, ge cpd and the rare earth compound one or more; Said polycondensation catalyst is preferably and is selected from titanium compound, antimony compounds, ge cpd, acetate, tin compound and the rare earth compound one or more.
More preferably, said acetate is to be selected from Cobaltous diacetate, manganese acetate, magnesium acetate, calcium acetate, zinc acetate, sodium-acetate, plumbic acetate, Burow Solution, cadmium acetate, antimony acetate and the Lithium Acetate one or more; Said titanium compound is to be selected from mixture, titanium oxide, tetrabutyl titanate, isopropyl titanate, metatitanic acid four different monooctyl esters, titanium potassium oxalate(T.P.O.), titanium ethylene glycolate and the butyleneglycol titanium of titanium oxide and the silicon-dioxide of titanium/silicon mol ratio between 9:1-1:9 one or more; Said antimony compounds is to be selected from Antimony Trioxide: 99.5Min, antimony acetate and the antimony glycol one or more; Said ge cpd is to be selected from germanium dioxide and the germanium chloride one or more; Said rare earth compound is to be selected from Lanthanum trichloride, hafnium chloride, rubidium chloride, Yttrium trichloride, methyl ethyl diketone lanthanum, methyl ethyl diketone hafnium, methyl ethyl diketone rubidium and the methyl ethyl diketone yttrium one or more; Said tin compound is to be selected from stannous octoate, stannous oxalate, butyl stannonic acid, Mono-n-butyltin and dibutyl-diethyl octanoate one or more.
More preferably, said polycondensation catalyst is to be selected from mixture, tetrabutyl titanate, isopropyl titanate, titanium oxide, Antimony Trioxide: 99.5Min, antimony acetate, Lithium Acetate, Burow Solution, Cobaltous diacetate, sodium-acetate, antimony glycol, germanium dioxide, germanium chloride, stannous octoate, stannous oxalate, Lanthanum trichloride, hafnium chloride, methyl ethyl diketone lanthanum and the methyl ethyl diketone hafnium of titanium oxide and the silicon-dioxide of titanium/silicon mol ratio between 9:1-1:9 one or more.
Said thermo-stabilizer is preferably phosphoric acid or phosphorons acid compound, and said auxiliary agent is preferably and is selected from lubricant, nucleator and C
3-C
12The aliphatics trivalent alcohol in one or more.
More preferably, said thermo-stabilizer is to be selected from phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate, trimethyl phosphite 99, triethyl phosphate, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triethyl-phosphite, triphenyl phosphite and the phosphorous acid diphenyl ester one or more; Said lubricant is to be selected from Triple Pressed Stearic Acid, stearate, paraffin and the stearic amide one or more; Said nucleator is to be selected from talcum, titanium oxide, silicon-dioxide, mica, polynite and the organic carboxylate one or more; Said C
3-C
12The aliphatics trivalent alcohol for being selected from 1,2,4-trihydroxybutane and 1,2, one or more in the 3-USP Kosher.
In aforesaid method, the speed of intensification and cooling all is preferably set to 5-10 ℃/min.
The consumption of the catalysts in the said step 1 is preferably the 0.005-5wt% of monomethyl succinate, more preferably 0.005-1wt%, most preferably 0.01-1wt%; The consumption of said polycondensation catalyst is preferably the 0.005-5wt% of monomethyl succinate, more preferably 0.01-1wt%, most preferably 0.1-1wt%; The consumption of said thermo-stabilizer is preferably the 0.001-0.5wt% of monomethyl succinate, more preferably 0.001-0.3wt%, most preferably 0.01-0.1wt%; The consumption of said auxiliary agent is preferably the 0.005-1wt% of monomethyl succinate, more preferably 0.005-0.5wt%, most preferably 0.01-0.5wt%.
The preparation method of poly butylene succinate provided by the invention (PBS); On the one hand; Can solve existing with Succinic Acid and 1, the 4-butyleneglycol be monomer prepare have in the PBS technology that esterification reaction rate is low, the Succinic Acid reaction not thoroughly, problem such as by product THF growing amount height.In addition, utilize method provided by the invention, the recyclable utilization of about 50% methyl alcohol in the by product, the added value of raising by product.On the other hand, the acidity of monomethyl succinate reduces corrosion on Equipment less than Succinic Acid, thereby reduces equipment maintenance cost, more helps industrialization production.Simultaneously, owing to do not use chainextender, can further enlarge the range of application of PBS degradative plastics in the food product pack field.
Embodiment
Provide embodiment below; But it is worthy of note that the present invention is not limited to these and implements example; The ordinary skill of this area to some nonessential change and adjustment that the present invention has done, still belongs to protection scope of the present invention according to the content of foregoing invention.
Except that specified otherwise, equipment used of the present invention and method are general equipment in this area and method.1515-2414 type gel permeation chromatography (GPC) appearance of PBS molecular weight and MWD coefficients by using U.S. Waters company is measured, and trichloromethane is a moving phase, and take-off rate is 1ml/min, and column temperature is 30 ° of C, and standard is a PS.PBS form and aspect (L value and b value) adopt the automatic color difference meter of the BYKGardner Color35 of company type to measure automatically.
Embodiment 1
Take by weighing monomethyl succinate 52.8g, 1 respectively, 4-butyleneglycol 43.2g, calcium acetate 0.01g, magnesium acetate 0.01g and zinc acetate 0.01g join in the 250ml there-necked flask, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 180 ℃; The reaction 1.5h after with temperature-programmed mode (temperature rise rate be 5 ℃/min) be warmed up to 220 ℃; Keep this thermotonus 150min can think that up to the 90wt% that water and methyl alcohol liquid outlet quantity reach theoretical value reaction finishes.With system cooling (rate of temperature fall be 10 ℃/min) to 150 ℃; When continuing logical nitrogen, remove water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to absolute pressure 5000Pa, reaction 20min participates in monomer and the by product that reacts in the removal system.Stop to vacuumize and feeding nitrogen, add mixture 0.25g (wherein the mass ratio of Antimony Trioxide: 99.5Min and methyl ethyl diketone lanthanum is 4:1), triphenyl phosphite 0.01g and the calcium stearate 0.01g of Antimony Trioxide: 99.5Min and methyl ethyl diketone lanthanum; Stir 15min and guarantee that catalyzer and auxiliary agent are dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the absolute pressure 50Pa, and be rapidly heated (temperature rise rate be 5 ℃/min) to 230 ℃, keep simultaneously stirring fast, isothermal reaction 240min under vacuum state (product viscosity increases and pole-climbing) promptly obtains product.Carrying out compression molding to product then carries out the form and aspect test or it is dissolved in chloroform then with carrying out molecular weight and MWD behind the methanol extraction.
The weight-average molecular weight of measuring product is 118600g/mol, and the MWD coefficient is 1.8, and colourity b value is 0.8.
Embodiment 2
Take by weighing monomethyl succinate 52.8g, 1 respectively, 4-butyleneglycol 50.4g and calcium acetate 0.05g join in the 250ml there-necked flask, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃ is carried out negative reaction (wherein, vacuum tightness is absolute pressure 6000Pa) and is kept this thermotonus 240min can think that up to the 90wt% that water and methyl alcohol liquid outlet quantity reach theoretical value reaction finishes under this temperature.Stop to vacuumize and feeding nitrogen, adding titanium/silicon mol ratio is the titanium oxide of 9:1 and mixture 0.15g, Lithium Acetate 0.02g, Cobaltous diacetate 0.005g, the triethyl-phosphite 0.01g of silicon-dioxide; Stir 15min and guarantee that catalyzer and auxiliary agent are dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the absolute pressure 30Pa, and be rapidly heated (temperature rise rate be 5 ℃/min) to 230 ℃, keep simultaneously stirring fast, isothermal reaction 120min under vacuum state (product viscosity increases and pole-climbing) promptly obtains product.Carrying out compression molding to product then carries out the form and aspect test or it is dissolved in chloroform then with carrying out molecular weight and MWD behind the methanol extraction.
The weight-average molecular weight of measuring product is 129700g/mol, and the MWD coefficient is 2.1, and colourity b value is 2.1.
Embodiment 3
Take by weighing monomethyl succinate 52.8g, 1 respectively, 4-butyleneglycol 43.2g and titanium oxide 0.02g join in the 250ml there-necked flask, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 150 ℃; The reaction 60min after with temperature-programmed mode (temperature rise rate be 5 ℃/min) be warmed up to 220 ℃; Keep this thermotonus 180min can think that up to the 90wt% that water and methyl alcohol liquid outlet quantity reach theoretical value reaction finishes.With system cooling (rate of temperature fall be 10 ℃/min) to 150 ℃; When continuing logical nitrogen, remove water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to absolute pressure 6000Pa, reaction 15min participates in monomer and the by product that reacts in the removal system.Stop to vacuumize and feeding nitrogen, add germanium dioxide 0.30g, triethyl-phosphite 0.02g, calcium stearate 0.01g and 1,2,3-USP Kosher 0.22g; Stir 15min and guarantee that catalyzer and auxiliary agent are dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the absolute pressure 50Pa, and be rapidly heated (temperature rise rate be 5 ℃/min) to 220 ℃, keep simultaneously stirring fast, isothermal reaction 240min under vacuum state (product viscosity increases and pole-climbing) promptly obtains product.Carrying out compression molding to product then carries out the form and aspect test or it is dissolved in chloroform then with carrying out molecular weight and MWD behind the methanol extraction.
The weight-average molecular weight of measuring product is 96300g/mol, and the MWD coefficient is 2.0, and colourity b value is 0.9.
Embodiment 4
Take by weighing monomethyl succinate 52.8g, 1 respectively, 4-butyleneglycol 39.6g and germanium dioxide 0.01g join in the 250ml there-necked flask, wherein connect stirring flatly, connect nitrogen protection flatly, and another mouth connects water trap and still column; Start stirring, reacting by heating system to 180 ℃; The reaction 90min after with temperature-programmed mode (temperature rise rate be 5 ℃/min) be warmed up to 220 ℃; Keep this thermotonus 150min can think that up to the 90wt% that water and methyl alcohol liquid outlet quantity reach theoretical value reaction finishes.With system cooling (rate of temperature fall be 10 ℃/min) to 145 ℃; When continuing logical nitrogen, remove water trap and prolong; Connect the vacuum pump interface; Close the channel of nitrogen valve and begin to be evacuated to absolute pressure 5000Pa, reaction 30min participates in monomer and the by product that reacts in the removal system.Stop to vacuumize and feeding nitrogen, adding titanium/silicon mol ratio is the titanium oxide of 1:4 and mixture 0.15g, methyl ethyl diketone lanthanum 0.02g, Lithium Acetate 0.01g, Cobaltous diacetate 0.005g, the triphenyl phosphite 0.02g of silicon-dioxide; Stir 20min and guarantee that catalyzer and auxiliary agent are dispersed in the reaction system.Stop logical nitrogen, be evacuated to below the absolute pressure 30Pa, and be rapidly heated to 230 ℃, keep simultaneously stirring fast, isothermal reaction 180min under vacuum state (product viscosity increases and pole-climbing) promptly obtains product.Carrying out compression molding to product then carries out the form and aspect test or it is dissolved in chloroform then with carrying out molecular weight and MWD behind the methanol extraction.
The weight-average molecular weight of measuring product is 109700g/mol, and the MWD coefficient is 1.8, and colourity b value is 1.7.
Claims (10)
1. the preparation method of a poly butylene succinate, this method comprises the steps:
Step 1, be benchmark with the monomethyl succinate monomer weight, with monomethyl succinate, 1,4-butyleneglycol and catalysts join in the reactor drum of protection of inert gas; Wherein, said monomethyl succinate and 1, the mol ratio of 4-butyleneglycol is 1:1-1:3; Arrive 150-220 ℃ with temperature-programmed mode temperature reaction system then; Keep this thermotonus 60-300min, be warmed up to 160-240 ℃ with temperature-programmed mode more afterwards, keep this thermotonus 80-180min to carry out synthesis under normal pressure; The 90wt% that reaches theoretical liquid outlet quantity up to the by product liquid outlet quantity thinks that promptly reaction finishes
Step 2, polycondensation; The reaction system that to carry out behind the synthesis under normal pressure cools to 140-150 ℃, connects vacuum system, is evacuated between the absolute pressure 1000-50000Pa; Reaction 15-30min; Remove monomer and the small molecule by-product of not participating in reaction in the reaction system, stop to vacuumize and feeding nitrogen, add polycondensation catalyst, thermo-stabilizer and auxiliary agent; Stir 10-30min and guarantee that catalyzer, thermo-stabilizer and auxiliary agent are dispersed in the reaction system; Stop logical nitrogen; Be evacuated to below the absolute pressure 100Pa, and be rapidly heated, keep simultaneously stirring fast to 200 ℃-240 ℃ of temperature of reaction; Isothermal reaction 60-240min promptly obtains product under vacuum state
Perhaps, this method comprises the steps:
Step 1, be benchmark with the monomethyl succinate monomer weight; With monomethyl succinate, 1,4-butyleneglycol and catalysts join in the reactor drum of protection of inert gas, wherein; Said monomethyl succinate and 1; The mol ratio of 4-butyleneglycol is 1:1-1:3, arrives 150-220 ℃ with temperature-programmed mode temperature reaction system then, keeps this thermotonus 10-300min to carry out negative reaction; Wherein the vacuum tightness of negative reaction remains between the absolute pressure 5000-20000Pa, and the 90wt% that reaches theoretical liquid outlet quantity up to the by product liquid outlet quantity thinks that promptly reaction finishes;
Step 2, polycondensation stop to vacuumize and feeding nitrogen behind the negative reaction, add polycondensation catalyst, thermo-stabilizer and auxiliary agent; Stir 10-30min and guarantee that polycondensation catalyst, thermo-stabilizer and auxiliary agent are dispersed in the reaction system; Stop logical nitrogen; Be evacuated to below the absolute pressure 100Pa; And be rapidly heated to 200 ℃-240 ℃ of temperature of reaction, keeping simultaneously stirring fast, isothermal reaction 60-240min promptly obtains product under vacuum state.
2. method according to claim 1, wherein, said monomethyl succinate and 1, the mol ratio of 4-butyleneglycol is 1:1-1:1.6.
3. method according to claim 1 and 2, wherein, the catalysts in the said step 1 is to be selected from acetate, titanium compound, antimony compounds, ge cpd and the rare earth compound one or more; Said polycondensation catalyst is to be selected from titanium compound, antimony compounds, ge cpd, acetate, tin compound and the rare earth compound one or more.
4. method according to claim 3, wherein, said acetate is to be selected from Cobaltous diacetate, manganese acetate, magnesium acetate, calcium acetate, zinc acetate, sodium-acetate, plumbic acetate, Burow Solution, cadmium acetate, antimony acetate and the Lithium Acetate one or more; Said titanium compound is to be selected from mixture, titanium oxide, tetrabutyl titanate, isopropyl titanate, metatitanic acid four different monooctyl esters, titanium potassium oxalate(T.P.O.), titanium ethylene glycolate and the butyleneglycol titanium of titanium oxide and the silicon-dioxide of titanium/silicon mol ratio between 9:1-1:9 one or more; Said antimony compounds is to be selected from Antimony Trioxide: 99.5Min, antimony acetate and the antimony glycol one or more; Said ge cpd is to be selected from germanium dioxide and the germanium chloride one or more; Said rare earth compound is to be selected from Lanthanum trichloride, hafnium chloride, rubidium chloride, Yttrium trichloride, methyl ethyl diketone lanthanum, methyl ethyl diketone hafnium, methyl ethyl diketone rubidium and the methyl ethyl diketone yttrium one or more; Said tin compound is to be selected from stannous octoate, stannous oxalate, butyl stannonic acid, Mono-n-butyltin and dibutyl-diethyl octanoate one or more.
5. method according to claim 4; Wherein, said polycondensation catalyst is to be selected from mixture, tetrabutyl titanate, isopropyl titanate, titanium oxide, Antimony Trioxide: 99.5Min, antimony acetate, Lithium Acetate, Burow Solution, Cobaltous diacetate, sodium-acetate, antimony glycol, germanium dioxide, germanium chloride, stannous octoate, stannous oxalate, Lanthanum trichloride, hafnium chloride, methyl ethyl diketone lanthanum and the methyl ethyl diketone hafnium of titanium oxide and the silicon-dioxide of titanium/silicon mol ratio between 9:1-1:9 one or more.
6. method according to claim 1 and 2, wherein, said thermo-stabilizer is phosphoric acid or phosphorons acid compound, said auxiliary agent is for being selected from lubricant, nucleator and C
3-C
12The aliphatics trivalent alcohol in one or more.
7. method according to claim 6; Wherein, said thermo-stabilizer is to be selected from phosphoric acid, phosphorous acid, ortho phosphorous acid, tetra-sodium, ammonium phosphate, trimethyl phosphite 99, triethyl phosphate, dimethyl phosphate, triphenylphosphate, diphenyl phosphate, triethyl-phosphite, triphenyl phosphite and the phosphorous acid diphenyl ester one or more; Said lubricant is to be selected from Triple Pressed Stearic Acid, stearate, paraffin and the stearic amide one or more; Said nucleator is to be selected from talcum, titanium oxide, silicon-dioxide, mica, polynite and the organic carboxylate one or more; Said C
3-C
12The aliphatics trivalent alcohol for being selected from 1,2,4-trihydroxybutane and 1,2, one or more in the 3-USP Kosher.
8. method according to claim 1 and 2, wherein, the speed of intensification and cooling all is set at 5-10 ℃/min.
9. method according to claim 1 and 2, wherein, the consumption of the catalysts in the said step 1 is the 0.005-5wt% of monomethyl succinate; The consumption of said polycondensation catalyst is the 0.005-5wt% of monomethyl succinate; The consumption of said thermo-stabilizer is the 0.001-0.5wt% of monomethyl succinate; The consumption of said auxiliary agent is the 0.005-1wt% of monomethyl succinate.
10. method according to claim 9, wherein, the consumption of the catalysts in the said step 1 is the 0.005-1wt% of monomethyl succinate, preferred 0.01-1wt%; The consumption of said polycondensation catalyst is the preferred 0.01-1wt% of monomethyl succinate, preferred 0.1-1wt%; The consumption of said thermo-stabilizer is the 0.001-0.3wt% of monomethyl succinate, preferred 0.01-0.1wt%; The consumption of said auxiliary agent is the 0.005-0.5wt% of monomethyl succinate, preferred 0.01-0.5wt%.
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| CN104761707A (en) * | 2015-04-14 | 2015-07-08 | 江苏钟腾化工有限公司 | Preparation method of polybutylene succinate |
| CN106008932A (en) * | 2016-07-19 | 2016-10-12 | 宁德师范学院 | Novel method for preparing poly(butylene succinate) through melt polycondensation |
| CN106279646A (en) * | 2016-08-23 | 2017-01-04 | 杭州鑫富科技有限公司 | A kind of heat-resisting poly butylene succinate and preparation method thereof |
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| CN113896868A (en) * | 2021-09-28 | 2022-01-07 | 天津工业大学 | Method for preparing polybutylene succinate by taking dimethyl succinate as raw material |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796435A (en) * | 2004-12-22 | 2006-07-05 | 中国科学院化学研究所 | Modified butanediol ester poly succinic acid and synthetic method |
-
2012
- 2012-07-09 CN CN201210237694.1A patent/CN102718949B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796435A (en) * | 2004-12-22 | 2006-07-05 | 中国科学院化学研究所 | Modified butanediol ester poly succinic acid and synthetic method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327466A (en) * | 2014-10-28 | 2015-02-04 | 山东中大药业有限公司 | Modified biodegradable plastic and preparation method thereof |
| CN104761707A (en) * | 2015-04-14 | 2015-07-08 | 江苏钟腾化工有限公司 | Preparation method of polybutylene succinate |
| CN104761707B (en) * | 2015-04-14 | 2016-08-31 | 江苏钟腾化工有限公司 | A kind of preparation method of poly butylene succinate |
| CN106008932A (en) * | 2016-07-19 | 2016-10-12 | 宁德师范学院 | Novel method for preparing poly(butylene succinate) through melt polycondensation |
| CN106279646A (en) * | 2016-08-23 | 2017-01-04 | 杭州鑫富科技有限公司 | A kind of heat-resisting poly butylene succinate and preparation method thereof |
| CN107365412A (en) * | 2017-08-27 | 2017-11-21 | 淄博长宝新材料股份有限公司 | The preparation method of biodegradable plastic poly butylene succinate |
| CN111384261A (en) * | 2018-12-28 | 2020-07-07 | Tcl集团股份有限公司 | Thin film and preparation method thereof and quantum dot light-emitting diode |
| CN111384261B (en) * | 2018-12-28 | 2021-08-10 | Tcl科技集团股份有限公司 | Thin film and preparation method thereof and quantum dot light-emitting diode |
| CN113292712A (en) * | 2021-05-25 | 2021-08-24 | 吉林建筑大学 | 1, 4-succinic acid-based copolyester material and preparation method and application thereof |
| CN113896868A (en) * | 2021-09-28 | 2022-01-07 | 天津工业大学 | Method for preparing polybutylene succinate by taking dimethyl succinate as raw material |
| CN114957628A (en) * | 2022-05-24 | 2022-08-30 | 珠海金发生物材料有限公司 | Polyester and preparation method and application thereof |
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