CN102268132A - Preparation method for polybutylene terephthalate lactic acid (PBTLA) copolymer - Google Patents
Preparation method for polybutylene terephthalate lactic acid (PBTLA) copolymer Download PDFInfo
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Abstract
The invention relates to a preparation method for PBTLA copolymer. The PBTLA copolymer is prepared by using terephthalic acid (or dimetyl terephthalate), butylene glycol and lactic acid monomers as raw materials and carrying out esterification (or ester interchange) under the action of a catalyst at first and polycondensation the next on the raw materials. According to the invention, no individual synthesis of lactic acid oligopolymers is needed, and lactic acid is directly inserted into chain segments of polybutylene terephthalate (PBT). The raw materials used in the preparation method are simple and cheap, and the preparation process is free of the step of synthesis of lactic acid oligopolymers; therefore, the preparation flow is shortened, production cost is reduced, and the obtained copolymer not only has good heat resistance and a machining property, but also has a certain degree of degradability. The copolymer prepared by the preparation method can be used in a wide variety of fields like degradable plastics, degradable fibers, degradable films, controlled release carriers of drugs, etc.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method of terephthalic acid butyleneglycol lactic acid copolymer.
Background technology
Plastics because of its preparation easily, relative low price and also have and be subjected to liking of people long work-ing life.Yet most of plastics are difficult to degraded under state of nature, are difficult for reclaiming in addition, are easy to produce a large amount of plastic garbages, cause serious environmental to pollute.
Polybutylene terephthalate (hereinafter to be referred as PBT) is because have crystallizing power fast, thereby make it have good processing characteristics, mechanical property and thermotolerance, it is a kind of general engineering plastic that is widely used in various fields, such as: injection moulded products such as trolley part, electronic and electric components, precision instrument parts also are widely used in fields such as film, sheet, monofilament, fibers in recent years.But PBT has high stability to hydrolysis in normal circumstances, is difficult to natural decomposition, therefore easily environment is polluted.The raw material of poly(lactic acid) (hereinafter to be referred as PLA)-monomer lactic origin is in renewable resources, as corn, paddy, potato and Ipomoea batatas etc.Poly(lactic acid) has good biodegradability, and it can be degraded fully by the occurring in nature microorganism after using, and finally generates carbonic acid gas and water, and is free from environmental pollution, highly beneficial to environment protection, helps developing low-carbon (LC) and recycling economy.It is not very desirable that but poly(lactic acid) causes its processing characteristics and mechanical property because of the crystallinity difference, thereby especially the resistance toheat difference of poly-lactic acid material has limited its application.
Therefore having some investigators to attempt developing can be in conjunction with the polymkeric substance of PBT and PLA characteristic, make it have both common advantages, promptly has degradability, the favorable mechanical performance is arranged again, the use of lactic acid simultaneously can reduce the dependence to petroleum resources again, and probably the polymkeric substance in conjunction with PBT and PLA characteristic is bound to have very big practical prospect.The method of simple possible is made multipolymer to PBT and PLA exactly.
The method for preparing PBT and PLA multipolymer in recent years has two big classes: a class is directly PBT and PLA to be carried out reactively blending to obtain the copolyesters product, Chinese patent CN200710051426.X for example, though this technology is easy and simple to handle, but this method is raw materials used is polymkeric substance rather than monomer, and the price of polymkeric substance will be much larger than monomer, so its raw materials cost is higher, and the PBT in the copolyesters that obtains with this method exists with the disconnected form of long-chain, the hydrolytic resistance of PBT own is fine, so these class methods are produced the copolyesters that obtains and can not be degraded basically, thereby influence its practical application; Another kind of is earlier the lactic acid monomer melt phase polycondensation to be become oligopolymer (being oligopolymer again), again the prepolymer of this oligopolymer and PBT is carried out the direct melt polycondensation reaction and obtain multipolymer, Chinese patent CN200810162341.3 for example, though this technology is easy and simple to handle, but lactic acid must react separately earlier and generate oligopolymer, then could be as reacting in the raw material adding system, do like this and can bring two problems: the one, because lactic acid oligomers is to embed multipolymer with longer chain forms, the resistance toheat of the multipolymer that obtains is descended; Two increase by a step and are used for the synthesizing lactic acid oligopolymer and can make Production Flow Chart become long and complicated specially in generative process, make the decrease in efficiency of production, and cost rises.
Summary of the invention
The objective of the invention is to overcome defective of the prior art, a kind of simple economy is provided, is easy to the preparation method of the terephthalic acid butyleneglycol lactic acid copolymer of suitability for industrialized production.This method is raw materials used cheap and easy to get, and synthetic route is brief, is easy to suitability for industrialized production, and can make multipolymer not only have good thermotolerance and machining property by the content of regulating lactic acid in the multipolymer, but also has certain degradation property.
The present invention realizes by the following method:
A kind of method for preparing terephthalic acid butyleneglycol lactic acid copolymer comprises following steps:
(1) with raw material 1, butyleneglycol and lactic acid monomer mix, and add catalyzer 1, at 160～230 ℃, carry out reaction in 0.5～5 hour under normal pressure or the decompression, thereby obtain prepolycondensate solution;
(2) in the precondensation solution that step (1) obtains, add catalyzer 2 and stablizer,, carry out 1～10 hour melt polycondensation reaction under 40～30000Pa, obtain the polybutylene terephthalate lactic acid copolymer at 180～250 ℃;
Wherein, raw material 1 is selected from terephthalic acid or dimethyl terephthalate (DMT); When raw material 1 was terephthalic acid, the reaction in the step (1) was the direct esterification reaction; When raw material 1 was dimethyl terephthalate (DMT), the reaction in the step (1) was direct transesterification reaction.
In the aforesaid method, under catalyst action, do not need earlier synthesizing lactic acid oligopolymer separately, just can directly be inserted into lactic acid in the polybutylene terephthalate, the fusion copolymerization obtains terephthalic acid butyleneglycol lactic acid copolymer.
In the raw material of the present invention, there is no particular limitation for lactic acid monomer, lactic acid monomer can be L-lactic acid, D-lactic acid, D, L-lactic acid or their any mixture, its form can be pure lactic acid, or lactic acid aqueous solution, if lactic acid aqueous solution uses preceding need vacuumizing through simple heating to remove free-water.
In the above-mentioned reaction, be not particularly limited for the ratio between the raw material, but consider that the difference because of mol ratio makes the rerum natura of product that actual application value can be arranged, so the mol ratio of qualification terephthalic acid and butyleneglycol preferably is between 1: 1～1: 4, the mol ratio of dimethyl terephthalate (DMT) and butyleneglycol preferably be between 1: 1～1: 4, the mol ratio of terephthalic acid and lactic acid monomer preferably be between 1: 10～10: 1, the mol ratio of dimethyl terephthalate (DMT) and lactic acid monomer preferably be between 1: 10～10: 1.
Among the above-mentioned preparation method, catalyzer 1 is selected from one or more in titanium compound, tin compound, oxyhydroxide or the acid; Described catalyzer 2 is selected from one or more in titanium compound, tin compound or the acid.Titanium compound, tin compound and acid in catalyzer 1 and the catalyzer 2 can be identical also can be inequality.Its amount ranges is considered factors such as speed of reaction, energy consumption, product shade, processing degradation, and the consumption of catalyzer 1 is preferably 0.001%～1% of terephthalic acid or dimethyl terephthalate (DMT) weight, is more preferably 0.01%～0.1%; The consumption of catalyzer 2 is preferably 0.001%～5% of terephthalic acid or dimethyl terephthalate (DMT) weight, is more preferably 0.01%～0.1%.
Above-mentioned titanium compound is selected from one or more in tetrabutyl titanate, metatitanic acid four isopropyl esters, titanium ethylene glycolate, titanium butoxide, titanium tetrachloride, metatitanic acid tetramethyl ester, potassium titanate, tetraethyl titanate, TiO 2 particles or the titanium dioxide and silicon dioxide composite particles.More preferably tetrabutyl titanate or TiO 2 particles most preferably are tetrabutyl titanate.
Tin compound is selected from one or more in tin protoxide, stannous octoate, tin protochloride, the inferior tin of lactic acid, three n-propyl tin acetic ester, dibutyl tin acetate or the Dibutyltin oxide.Most preferably be tin protochloride.
Oxyhydroxide is selected from one or more in magnesium hydroxide, calcium hydroxide, potassium hydroxide or the sodium hydroxide.Most preferably be magnesium hydroxide.
Acid is selected from one or more in sulfuric acid, phosphoric acid, metatitanic acid, methylsulphonic acid or the toluene sulfonic acide.More preferably methylsulphonic acid or toluene sulfonic acide most preferably are toluene sulfonic acide.
The present invention prepares in the method for terephthalic acid butyleneglycol lactic acid copolymer, the stablizer that in step (2) process, adds, there is no particular limitation for stablizer among the present invention, as long as can play the content of carboxyl end group effect of inhibition system yellowing and minimizing multipolymer, consider because of adding other stablizers to make other mis-behaves of multipolymer, thereby stablizer is preferably in hindered phenolic, phosphoric acid ester or the phosphorous acid esters commonly used in polyester one or more; Consider the effect of stablizer and to the performance impact of product, the total amount of stablizer is preferably 0.01%～1.0% of raw material terephthalic acid or dimethyl terephthalate (DMT) weight.
Stablizer is four (methylene radical 3-3 ' more preferably, 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester methane (Irganox1010), 3, one or more in 5-di-t-butyl-4-hydroxyphenyl diethyl phosphoric acid (Irganox1222), triphenylphosphate, trimethyl phosphite 99, triethyl phosphate or the triphenyl phosphite.Stablizer can be when step (1) finishes, adds when promptly precondensation finishes in the reactor, and can be arbitrary constantly in the polycondensation process to add in the reactor also in step (2).
The present invention prepares the method for terephthalic acid butyleneglycol lactic acid copolymer, in order further to improve the molecular weight of product, in step (2) is after melt polycondensation reaction finishes, can increase the molecular weight (being solid-phase tack producing) of multipolymer by solid state polycondensation, by solid-phase tack producing the weight-average molecular weight of multipolymer is reached more than 100,000, even can reach 300,000.The concrete enforcement of solid state polycondensation is as follows: earlier after room temperature or following melt phase polycondensation product pulverizing of freezing state granulation to mean particle size are 0.01mm～5mm, carry out tackify by solid state polycondensation then; Wherein the solid state polycondensation temperature is 150～210 ℃, 2～40 hours time.During solid phase polycondensation, the rare gas element state that reaction is in vacuum state or is flowing, reactor vacuum tightness is less than 133Pa during vacuum state.In order to reach better tackify effect, the mean particle size of pulverizing granulation is preferably 0.5-4mm.
Advantage of the present invention is: by terephthalic acid (or dimethyl terephthalate (DMT)), butyleneglycol and three kinds of monomers of lactic acid are carried out direct copolymerization, avoided traditional reactive blend method need with more expensive polymkeric substance as raw material and because multipolymer in long two shortcomings that make multipolymer be difficult to degrade of PBT segment; Also deducted on production technique and be used for the step of synthesizing lactic acid oligopolymer specially, thereby Production Flow Chart is shortened, cost obviously descends.The raw materials used cheap and simple of this method, synthetic route is brief, is easy to suitability for industrialized production, and can make multipolymer not only have good thermotolerance and machining property by the content of reconciling lactic acid in the multipolymer, but also has certain degradation property.
The terephthalic acid butyleneglycol lactic acid copolymer that uses this method to obtain can be widely used in fields such as degradable plastics, biodegradable fiber, degradable films, drug controllable release carrier.
Embodiment
Below, by embodiment the present invention is described in more detail, but the present invention is only otherwise exceed its main points, then is not subjected to any restriction of following examples.In addition, below in each example raw material sources and employed physical property measurement method as follows:
Terephthalic acid (chemical pure), dimethyl terephthalate (DMT) (chemical pure), 1,4-butyleneglycol (chemical pure), tetrabutyl titanate (analytical pure), titanium isopropylate (analytical pure) and stablizer are all available from Chemical Reagent Co., Ltd., Sinopharm Group; Lactic acid (90% the aqueous solution, carry out before the use simple heating vacuumize remove free-water) available from Jiangxi Musashi wildlife chemical industry company limited.
The weight-average molecular weight of multipolymer adopts gel permeation chromatography (GPC) to characterize, and chloroform is as moving phase, 40 ℃ of probe temperatures, and chloroform and hexafluoroisopropanol combination solution (v/v=9/1) are as the solvent of this multipolymer of dissolving.
That injector is selected for use is the EIject NEX 1000 of Japan's day smart Plastics Industry Company production.Mould therefor is that mould is used in the iso standard test, and injecting condition is: injection temperature is 220 ℃, and die temperature is 40 ℃, 40 seconds cooling times.
The tensile property test is according to ISO 527-1:1993, and with AG-IS (20KN) the SHIMADZU tensile testing machine test that day island proper Tianjin company produces, test result is got the mean value of six samples.
The bending property test is according to ISO 178-1975, and with AG-IS (5KN) the SHIMADZU flexing machine test that day island proper Tianjin company produces, test result is got the mean value of six samples.
The notch shock performance test is tested with the No.258-DIMPACT Tester test with notched test piece machine that the smart mechanism in day intrinsic safety field is done to be produced according to ISO 179-1:2000, and test result is got the mean value of six samples.
The second-order transition temperature of multipolymer and fusing point are to obtain by the DSC test, and test condition is: 20 ℃/min ,-40 ℃ to 230 ℃, the DSC Q100 mistake of producing with U.S. TA company scans the calorimeter test.
5% thermal weight loss temperature of multipolymer is to obtain by the TGA test, and test condition is: 20 ℃/min, 25 ℃ to 600 ℃, test with the SDT Q600 thermogravimetric analyzer that U.S. TA company produces.
Embodiment 1
With 400g dimethyl terephthalate (DMT) (DMT), 278.5g 1; that 4-butyleneglycol (BDO), 92.7g L-lactic acid (L-LA) (material molar ratio DMT: BDO: L-LA=1: 1.5: 0.5) join belt stirrer and be connected with in the reactor of flowing nitrogen protection; be warming up to 180 ℃ earlier; and kept this temperature 2 hours; add 0.2g metatitanic acid four isopropyl esters then; be warming up to 200 ℃, carried out esterification under the normal pressure 3 hours.After esterification finishes, adding 0.2g metatitanic acid four isopropyl esters and 0.8g stablizer four (methylene radical 3-3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester methane, is precondensation 2 hours under the condition of 20-50mmHg at 200 ℃ and pressure; Continue to reduce pressure to 0.75mmHg, and elevated temperature to 230 ℃, melt polycondensation reaction is 8 hours under this temperature, can make terephthalic acid butyleneglycol lactic acid copolymer (PBTLA), and the weight-average molecular weight that records through gel permeation chromatography (GPC) is 53371.At last this multipolymer is carried out injection molding, and carry out calorifics and Mechanics Performance Testing, test result sees Table 1.
Embodiment 2
With 400g dimethyl terephthalate (DMT) (DMT), 278.5g 1; that 4-butyleneglycol (BDO), 92.7g L-lactic acid (L-LA) (material molar ratio DMT: BDO: L-LA=1: 1.5: 0.5) join belt stirrer and be connected with in the reactor of flowing nitrogen protection; be warming up to 180 ℃ earlier; and kept this temperature 2 hours; add the 0.2g tetrabutyl titanate then; be warming up to 200 ℃, carried out esterification under the normal pressure 2 hours.After esterification finishes, add 0.1g nano-titania particle and 0.8g stablizer four (methylene radical 3-3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester methane, at 200 ℃, pressure is precondensation 2 hours under the condition of 20-50mmHg; Continue to reduce pressure to 0.75mmHg, and elevated temperature to 230 ℃, continued melt polycondensation reaction 4 hours, can make the polybutylene terephthalate lactic acid copolymer, recording its weight-average molecular weight through GPC is being 24352.With this polycondensation sample powder is pure become particle diameter to be the powder of 0.5-1.5mm after, carry out solid state polycondensation.The vacuum degree control of solid state polycondensation and is ceaselessly stirred reactant in case reactant is bonded to one another below 1mmHg, also need adopt the method heating that progressively heats up, heating schedule is: 90 ℃ were reacted 1 hour, 130 ℃ were reacted 1 hour, and 185 ℃ were reacted 1 hour, and 195 ℃ were reacted 20 hours.The weight-average molecular weight that the final terephthalic acid butyleneglycol lactic acid copolymer (PBTLA) that obtains records through GPC is 106727.This solid phase polycondensation product is carried out injection molding, and carry out calorifics and Mechanics Performance Testing, test result sees Table 1.
Embodiment 3
With 342.2g terephthalic acid (TPA), 278.5g 1,4-butyleneglycol (BDO), 92.7g L-lactic acid (L-LA) (material molar ratio TPA: BDO: L-LA=1: 1.5: 0.5) join in the voltage-resistant reactor of belt stirrer, earlier with the air in the nitrogen replacement reactor, be warming up to 180 ℃ and kept this temperature 2 hours earlier, pressure-controlling is at 70KPa～101KPa, add the 0.2g nano-titania particle then, be warming up to 200 ℃, carried out esterification under the normal pressure 2 hours.After esterification finishes, add 0.2mg nano-titania particle and 0.8g stablizer four (methylene radical 3-3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester methane, at 200 ℃, pressure is precondensation 2 hours under the condition of 20-50mmHg; Continue to reduce pressure to 0.75mmHg, and elevated temperature to 230 ℃, continued melt polycondensation reaction 5 hours, can make terephthalic acid butyleneglycol lactic acid copolymer, recording its weight-average molecular weight through GPC is being 23350.With this polycondensation sample powder is pure become particle diameter to be the powder of 0.5-1.5mm after, carry out solid state polycondensation.The vacuum degree control of solid state polycondensation and is ceaselessly stirred reactant in case reactant is bonded to one another below 1mmHg, also need adopt the method heating that progressively heats up, heating schedule is: 90 ℃ were reacted 1 hour, 130 ℃ were reacted 1 hour, and 185 ℃ were reacted 1 hour, and 195 ℃ were reacted 40 hours.The weight-average molecular weight that the final terephthalic acid butyleneglycol lactic acid copolymer (PBTLA) that obtains records through GPC is 202680.This solid phase polycondensation product is carried out injection molding, and carry out calorifics and Mechanics Performance Testing, test result sees Table 1.
Embodiment 4
With 342.2g terephthalic acid (TPA), 278.5g 1,4-butyleneglycol (BDO), 185.4g L-lactic acid (L-LA) (material molar ratio TPA: BDO: L-LA=1: 1.5: 1) join in the reactor of belt stirrer, earlier with the air in the nitrogen replacement reactor, be warming up to 180 ℃ and kept this temperature 1 hour earlier, pressure-controlling is at 70KPa～101KPa, add the 0.2g nano-titania particle then, be warming up to 200 ℃, carried out esterification under the normal pressure 3 hours.After esterification finishes, add 0.2g nano-titania particle and 0.8g stablizer four (methylene radical 3-3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester methane, at 200 ℃, pressure is precondensation 2 hours under the condition of 10-50mmHg; Continue to reduce pressure to 0.75mmHg, and elevated temperature to 225 ℃, continued melt polycondensation reaction 5 hours, can make terephthalic acid butyleneglycol lactic acid copolymer, recording its weight-average molecular weight through GPC is being 11317.With this polycondensation sample powder is pure become particle diameter to be the powder of 0.5-1.5mm after, carry out solid state polycondensation.The vacuum degree control of solid state polycondensation is below 1mmHg, and ceaselessly stir reactant in case reactant is bonded to one another, also need adopt the method heating that progressively heats up, heating schedule is: 90 ℃ were reacted 1 hour, 130 ℃ were reacted 2 hours, 150 ℃ were reacted 2 hours, and 180 ℃ were reacted 5 hours, and 190 ℃ were reacted 24 hours.The weight-average molecular weight that the final terephthalic acid butyleneglycol lactic acid copolymer (PBTLA) that obtains records through GPC is 48726.This solid phase polycondensation product is carried out injection molding, and carry out calorifics and Mechanics Performance Testing, test result sees Table 1.
Embodiment 5
With 400g dimethyl terephthalate (DMT) (DMT), 278.5g 1; that 4-butyleneglycol (BDO), 185.4g L-lactic acid (L-LA) (material molar ratio DMT: BDO: L-LA=1: 1.5: 1) join belt stirrer and be connected with in the reactor of flowing nitrogen protection; be warming up to 180 ℃ and kept this temperature 2 hours earlier; pressure is normal pressure; add the 0.4g tetrabutyl titanate then; be warming up to 200 ℃, carried out esterification under the normal pressure 4 hours.After esterification finishes, add 0.4g tetrabutyl titanate and 0.8g stablizer four (methylene radical 3-3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester methane, at 200 ℃, pressure is precondensation 2 hours under the condition of 10-50mmHg; Continue to reduce pressure to 0.75mmHg, and elevated temperature to 225 ℃, continued melt polycondensation reaction 5 hours, can make terephthalic acid butyleneglycol lactic acid copolymer, recording its weight-average molecular weight through GPC is being 12205.With this polycondensation sample powder is pure become particle diameter to be the powder of 0.5-1.5mm after, carry out solid state polycondensation.The vacuum degree control of solid state polycondensation is below 1mmHg, and ceaselessly stir reactant in case reactant is bonded to one another, also need adopt the method heating that progressively heats up, heating schedule is: 90 ℃ were reacted 1 hour, 130 ℃ were reacted 2 hours, 150 ℃ were reacted 2 hours, and 180 ℃ were reacted 5 hours, and 190 ℃ were reacted 35 hours.The weight-average molecular weight that the final terephthalic acid butyleneglycol lactic acid copolymer (PBTLA) that obtains records through GPC is 83386.This solid phase polycondensation product is carried out injection molding, and carry out calorifics and Mechanics Performance Testing, test result sees Table 1.
Comparative example 1
Earlier with 185.4g lactic acid at 150 ℃, pressure obtains lactic acid prepolymer by the dehydration polycondensation 8 hours of progressively reducing pressure under the condition of reaction end of a period 500Pa of the normal pressure of initial reaction stage.With 342.2 gram terephthalic acids, 278.5g 1,4-butyleneglycol (material molar ratio TPA: BDO: L-LA=1: 1.5: 1), 0.4 the gram tetrabutyl titanate adds the reactor that band stirs, at 200 ℃ of synthesis under normal pressure 1h, and 210 ℃ of synthesis under normal pressure 0.5h, 220 ℃ of synthesis under normal pressure 0.5h, keep temperature-resistant reduction pressure to 20000Pa, continue reaction 3h, promptly obtain the dibutyl terephthalate prepolymer.The lactic acid prepolymer that obtains joined carry out melt polycondensation reaction in the dibutyl terephthalate prepolymer, add 0.4 gram tetrabutyl titanate and 0.8g stablizer four (methylene radical 3-3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester methane, at 200 ℃, pressure is precondensation 2 hours under the condition of 10-50mmHg; Continue to reduce pressure to 0.75mmHg, and elevated temperature to 225 ℃, continued melt polycondensation reaction 5 hours, can make terephthalic acid butyleneglycol lactic acid copolymer, recording its weight-average molecular weight through GPC is being 8317.With this polycondensation sample powder is pure become particle diameter to be the powder of 0.5-1.5mm after, carry out solid state polycondensation.The vacuum degree control of solid state polycondensation is below 1mmHg, and ceaselessly stir reactant in case reactant is bonded to one another, also need adopt the method heating that progressively heats up, heating schedule is: 90 ℃ were reacted 1 hour, 130 ℃ were reacted 2 hours, 150 ℃ were reacted 2 hours, 170 ℃ of reactions 24 hours (because gained melt phase polycondensation product can't carry out solid state reaction because of fusing point is too low more than 170 ℃).The weight-average molecular weight that the final terephthalic acid butyleneglycol lactic acid copolymer (PBTLA) that obtains records through GPC is 28726.This solid phase polycondensation product can't carry out injection molding because of molecular weight is too low, can only carry out the thermal property test, and test result sees Table 1.
Comparative example 2
Earlier with 46.4g lactic acid at 150 ℃, pressure obtains lactic acid prepolymer by the dehydration polycondensation 8 hours of progressively reducing pressure under the condition of reaction end of a period 500Pa of the normal pressure of initial reaction stage.With 342.2 gram terephthalic acids, 278.5g 1,4-butyleneglycol (material molar ratio TPA: BDO: L-LA=1: 1.5: 0.25), 0.4 the gram tetrabutyl titanate adds the reactor that band stirs, at 200 ℃ of synthesis under normal pressure 1h, and 210 ℃ of synthesis under normal pressure 0.5h, 220 ℃ of synthesis under normal pressure 0.5h, keep temperature-resistant reduction pressure to 20000Pa, continue reaction 3h, promptly obtain the dibutyl terephthalate prepolymer.The lactic acid prepolymer that obtains joined carry out melt polycondensation reaction in the dibutyl terephthalate prepolymer, add 0.4 gram tetrabutyl titanate and 0.8g stablizer four (methylene radical 3-3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester methane, at 200 ℃, pressure is precondensation 2 hours under the condition of 10-50mmHg; Continue to reduce pressure to 0.75mmHg, and elevated temperature to 230 ℃, continued melt polycondensation reaction 5 hours, can make terephthalic acid butyleneglycol lactic acid copolymer, recording its weight-average molecular weight through GPC is being 15317.With this polycondensation sample powder is pure become particle diameter to be the powder of 0.5-1.5mm after, carry out solid state polycondensation.The vacuum degree control of solid state polycondensation is below 1mmHg, and ceaselessly stir reactant in case reactant is bonded to one another, also need adopt the method heating that progressively heats up, heating schedule is: 90 ℃ were reacted 1 hour, 130 ℃ were reacted 2 hours, 150 ℃ were reacted 2 hours, and 180 ℃ were reacted 5 hours, and 190 ℃ were reacted 24 hours.The weight-average molecular weight that the final terephthalic acid butyleneglycol lactic acid copolymer (PBTLA) that obtains records through GPC is 68726.This solid phase polycondensation product is carried out injection molding, and carry out calorifics and Mechanics Performance Testing, test result sees Table 1.
According to the productive rate of method synthetic copolyesters provided by the invention greater than 95% (weight of final product is divided by the weight of terephthalic acid or dimethyl terephthalate (DMT)), product colour is along with the increase of lactic acid monomer content becomes little Huang from milky white, and the transparency of product becomes transparent along with the increase of lactic acid monomer content is opaque again.
The calorifics and the mechanical property of the copolyesters that obtains of embodiment 1, embodiment 2 and embodiment 3 are obviously good than pure poly(lactic acid) (PLA) as can be drawn from Table 1, (PBT) is poor slightly than pure butylene terephthalate, consider its over-all properties, the multipolymer that obtains among these three embodiment can use at degradable plastics and biodegradable fiber field.
And the embodiment 4 from table 1, the copolyesters that can draw high lactic acid monomer content on elongation at break apparently higher than pure PLA and PBT, tensile strength and modulus in flexure then sharply descend, reason is along with a large amount of lactic acid units is embedded in the segment of PBT, increased the degree of randomness of copolyesters, reduced the degree of crystallinity and the resistance to hydrolysis of copolyesters, made this multipolymer become soft and easily degraded, so consider its over-all properties, the multipolymer that obtains among the embodiment 4 can use in the degradable films field.
Comparative example 1 and comparative example 2 are independent synthesizing lactic acid prepolymer and butylene terephthalate prepolymer, and then they mixing, compare in the present invention direct esterification or directly ester exchange method reaching how consuming time at least more than 8 hours on the same effect, but also consume energy more.Comparative example 1 from table 1, we can learn that the copolyesters that melt phase polycondensation obtains is too low because of fusing point, can't at high temperature carry out solid state reaction, so the copolyesters molecular weight that finally obtains less than 30,000, can not injection molding.And the copolyesters that obtains is difficult to crystallization, thereby do not have fusing point because be amorphous state completely, has only the melting range of a broadness.The copolyesters that the lactic acid content that hence one can see that obtains by this method is high is difficult to forming process, so can not use in degradable plastics, fiber and film field substantially.And in the comparative example 2, because lactic acid content reduces to 1/4th of comparative example 1, thus the copolyesters of high component can be obtained, and can injection molding.But because of lactic acid content very little, can make the performance of the copolyesters that obtains by this method not have much differences like this with pure PBT, so just lose the meaning of adding lactic acid, the while has also lost the meaning of PBT and PLA being made copolyesters.
Table 1.PBT, the calorifics of PLA and PBTLA and mechanical property
(performance of listed PLA and PBT is used for contrast in the table, and wherein PLA is the 4032D of Natureworks company production, and PBT is the 1100M that Toray company produces."/" expression is not because of obtaining sample, this data disappearance.)
Claims (8)
1. method for preparing terephthalic acid butyleneglycol lactic acid copolymer is characterized in that: comprise following steps:
(1) with raw material 1, butyleneglycol and lactic acid monomer mix, and add catalyzer 1, at 160～230 ℃, carry out reaction in 0.5～5 hour under normal pressure or the decompression, thereby obtain prepolycondensate solution;
(2) in the precondensation solution that step (1) obtains, add catalyzer 2 and stablizer,, carry out 1～10 hour melt polycondensation reaction under 40～30000Pa, obtain the polybutylene terephthalate lactic acid copolymer at 180～250 ℃;
Wherein, raw material 1 is selected from terephthalic acid or dimethyl terephthalate (DMT); When raw material 1 was terephthalic acid, the reaction in the step (1) was the direct esterification reaction; When raw material 1 was dimethyl terephthalate (DMT), the reaction in the step (1) was direct transesterification reaction.
2. the method for preparing the polybutylene terephthalate lactic acid copolymer according to claim 1, it is characterized in that: the mol ratio of terephthalic acid and butyleneglycol is between 1: 1～1: 4, the mol ratio of dimethyl terephthalate (DMT) and butyleneglycol is between 1: 1～1: 4, the mol ratio of terephthalic acid and lactic acid monomer is between 1: 10～10: 1, and the mol ratio of dimethyl terephthalate (DMT) and lactic acid monomer is between 1: 10～10: 1.
3. the method for preparing the polybutylene terephthalate lactic acid copolymer according to claim 1 is characterized in that: described catalyzer 1 is selected from one or more in titanium compound, tin compound, oxyhydroxide or the acid; Described catalyzer 2 is selected from one or more in titanium compound, tin compound or the acid.
4. the method for preparing the polybutylene terephthalate lactic acid copolymer according to claim 3 is characterized in that: described titanium compound is selected from one or more in tetrabutyl titanate, metatitanic acid four isopropyl esters, titanium ethylene glycolate, titanium butoxide, titanium tetrachloride, metatitanic acid tetramethyl ester, potassium titanate, tetraethyl titanate, TiO 2 particles or the titanium dioxide and silicon dioxide composite particles; Described tin compound is selected from one or more in tin protoxide, stannous octoate, tin protochloride, the inferior tin of lactic acid, three n-propyl tin acetic ester, dibutyl tin acetate or the Dibutyltin oxide; Described oxyhydroxide is selected from one or more in magnesium hydroxide, calcium hydroxide, potassium hydroxide or the sodium hydroxide; Described acid is selected from one or more in sulfuric acid, phosphoric acid, metatitanic acid, methylsulphonic acid or the toluene sulfonic acide.
5. according to each described method for preparing the polybutylene terephthalate lactic acid copolymer in the claim 1,3 or 4, it is characterized in that: the consumption of catalyzer 1 is 0.001%～1% of terephthalic acid or a dimethyl terephthalate (DMT) weight; The consumption of catalyzer 2 is 0.001%～5% of terephthalic acid or a dimethyl terephthalate (DMT) weight.
6. the method for preparing the polybutylene terephthalate lactic acid copolymer according to claim 1, it is characterized in that: the stablizer that in step (2), adds, described stablizer is selected from one or more in hindered phenolic, phosphoric acid ester or the phosphorous acid esters; Wherein, the total amount of stablizer is 0.01%～1.0% of raw material terephthalic acid or a dimethyl terephthalate (DMT) weight.
7. the method for preparing the polybutylene terephthalate lactic acid copolymer according to claim 6, it is characterized in that: stablizer is selected from four (methylene radical 3-3 ', 5 '-di-t-butyl-4-hydroxyphenyl) propionic ester methane, 3, one or more in 5-di-t-butyl-4 hydroxyphenyl diethyl phosphoric acid, triphenylphosphate, trimethyl phosphite 99, triethyl phosphate or the triphenyl phosphite.
8. the method for preparing the polybutylene terephthalate lactic acid copolymer according to claim 1 and 2, it is characterized in that: after the reaction of step (2), it is 0.01mm～5mm that product is pulverized granulation to mean particle size, carries out tackify by solid state polycondensation then; Wherein the solid state polycondensation temperature is 150～210 ℃, 2～40 hours time.
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| CN102643418A (en) * | 2012-04-20 | 2012-08-22 | 北京化工大学 | Method for preparing polylactic acid from lactic acid under catalysis of titanium composite catalyst |
| CN105419769A (en) * | 2015-11-05 | 2016-03-23 | 中国石油天然气股份有限公司 | Degradable fiber, fracturing fluid with same and method for preparing fracturing fluid |
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| CN115124702A (en) * | 2021-03-26 | 2022-09-30 | 华润化学材料科技股份有限公司 | Degradable aromatic-aliphatic copolyester material and preparation method and application thereof |
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2010
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643418A (en) * | 2012-04-20 | 2012-08-22 | 北京化工大学 | Method for preparing polylactic acid from lactic acid under catalysis of titanium composite catalyst |
| CN102643418B (en) * | 2012-04-20 | 2014-05-14 | 北京化工大学 | Method for preparing polylactic acid from lactic acid under catalysis of titanium composite catalyst |
| CN105419769A (en) * | 2015-11-05 | 2016-03-23 | 中国石油天然气股份有限公司 | Degradable fiber, fracturing fluid with same and method for preparing fracturing fluid |
| CN105419769B (en) * | 2015-11-05 | 2018-11-16 | 中国石油天然气股份有限公司 | A kind of preparation method of biodegradable fiber and fracturing fluid and the fracturing fluid containing it |
| CN109696343A (en) * | 2019-02-25 | 2019-04-30 | 湖南博隽生物医药有限公司 | A kind of hydrophilic glass slide and preparation method thereof |
| CN115124702A (en) * | 2021-03-26 | 2022-09-30 | 华润化学材料科技股份有限公司 | Degradable aromatic-aliphatic copolyester material and preparation method and application thereof |
| CN115677992A (en) * | 2021-07-27 | 2023-02-03 | 中国科学院理化技术研究所 | All-natural domain degradable aromatic materials aliphatic polyester polymer and process for producing the same |
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