CN103304787A - Polysebacic acid 1, 3-propylene glycol ester-block-polysuccinic acid butanediol block polyester and preparation method and use thereof - Google Patents
Polysebacic acid 1, 3-propylene glycol ester-block-polysuccinic acid butanediol block polyester and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to polysebacic acid 1, 3-propylene glycol ester-block-polysuccinic acid butanediol block polyester, wherein the general formula is shown in the specification, the molecular weight is in a range from 10000 to 50000. The molecular weight of the polyester provided by the invention is in the range from 10000 to 50000, the thermodynamic property of the polyester is equivalent to that of PBS (Polybutylene Succinate), the degradation performance is remarkably improved, the melting point is greater than 100 DEG C, the thermal stability is better, and the processing space is wider, so that the polyester can be used in the field of high molecular materials such as food package, agricultural plastic mulching films and medical sutures, and has a wide application prospect.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of poly-sebacic acid 1, ammediol ester (PPS)-block-poly butylene succinate (PBS) block polyester (PPS-block-PBS) and its production and use.
Background technology
In recent years; raising along with people's environmental consciousness; replace non-biodegradable material to become main flow trend with Biodegradable material; the overwhelming majority has replaced to the new bio degradation material in environment protection material and the packaging vessel material; especially on disposable product, the application of Biodegradable material is more extensive.In the new medical material field in some forward positions, Biodegradable material also has very big application potential.
Aliphatic polyester is the biodegradable material that a class forms through synthetic prepared, wherein, succinic acid-butanediol ester (PBS) is the Biodegradable material of generally acknowledging, its mechanical property excellence, can compare favourably with traditional plastics, fusing point surpasses 100 ℃, has good processing properties at normal temperatures, is to study comparatively ripe Biodegradable material.PBS base biodegradation plastics are as the packaging material for food of degradability, agricultural mulching, medicine equipment etc.; the theory that meets environment protection and the strategy of sustainable development; have a extensive future; but because the degree of crystallinity of PBS own is higher; it is longer to show as degradation time in actual applications, and degradation rate is not high.At present, the problem that needs to solve is to have under the prerequisite of equal performance in maintenance and conventional plastic, realizes the controllability to its degradation behavior, improves its degradation rate, makes PBS base biodegradation plastics adapt to the requirement of various applied environments, further reduces production costs.Select for use reproducible bio-based monomer that it is carried out modification, really realize industrialization, mass-producing, satisfy the demand in market.
Block modified research refers to be linked to each other and the new polymkeric substance that forms by the sequence monomer of two or more different chemical structures, i.e. segmented copolymer, and wherein each sequence is called as a block.The preparation process of block copolymer can effectively be controlled polymer chain length, structure sequence etc., reaches the purpose of molecular designing.On structure, soft section of forming segmented copolymer is different with hard section, and soft section and the hard intersegmental chemical incompatibility that exists have self peculiar property on the molecular chain arrangement architecture, different with homopolymer at aspects such as SOLUTION PROPERTIES, microphase-separated forms.Aspect theory research, because the regularity of block copolymer chain alignment, researcher is stronger to the modification purpose of molecular chain structure, and achievement in research has more theory directive significance.In application facet, segmented copolymer is as ampholyte copolymer, takes into account the soft section characteristic with hard section, can be used for strengthening the co-mixing system interface compatibility, improves the blend effect, and block polymer has been widely used in fields such as biology, bionical, medical treatment and nano material.
At present, aliphatic polyester still fails to be used alone as in the macromolecular material goods such as food product pack, agricultural mulching, suture, and reason is that their fusing point is lower.Generally speaking, fusing point is higher than 100 ℃, Drawing abillity and physicals have more use value, and poly butylene succinate is one of minority high melting point polyester, and fusing point can reach 115 ℃, but the spherulite size of PBS is bigger, degree of crystallinity is higher, and material is crisp, and spinning property is poor, synthetic cost is higher, is hindered in large-scale promotion.Poly-sebacic acid 1, the fusing point of ammediol (PPS) is about 60 ℃, but its degree of crystallinity is not high, segment has certain toughness, some performance can with the PBS complementation, and, the PPS synthon all derives from renewable plant resources, meets resources conservation, eco-friendly development trend.
By retrieval, do not find the patent publication us relevant with patent application of the present invention as yet.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, provide a kind of thermomechanical property and PBS suitable, degradation property significantly improves, fusing point is higher than 100 ℃, better heat stability, the poly-sebacic acid 1 that has wideer processing space and have wide application prospects, ammediol ester-block-poly butylene succinate block polyester, its preparation method technology is simple, environmental protection, be easy to control, reduced production cost, be easy to suitability for industrialized production, can be used for making in the macromolecular material goods fields such as food product pack, agricultural mulching, suture.
The present invention realizes that the technical scheme of purpose is:
A kind of poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester, this poly-sebacic acid 1, the general formula of ammediol ester-block-poly butylene succinate block polyester is as follows:
Aforesaid poly-sebacic acid 1, the preparation method of ammediol ester-block-poly butylene succinate block polyester, step is as follows:
⑴ gather sebacic acid 1, the preparation of ammediol ester prepolymer: with Succinic Acid and butyleneglycol in Succinic Acid: the amount of substance of butyleneglycol is than placing reactor for the ratio of 1:1～1:1.5, at N
2Protection is warming up to 160～180 ℃ down, after the complete fusion of monomer, carries out constant temperature and stirs esterification 1～5h, after reaction finishes, obtains poly-sebacic acid 1, ammediol ester prepolymer;
⑵ the preparation of poly butylene succinate prepolymer: with sebacic acid and 1, ammediol is pressed sebacic acid: 1, and the amount of substance of ammediol is than placing reactor for the ratio of 1:1～1:1.5, at N
2Protection down, be warming up to 160～180 ℃, after the complete fusion of monomer, carry out constant temperature and stir esterification, esterification 1～5h, after esterification finished, 160～200 ℃, vacuum ranges were to heat up under the condition of 50～500Pa to vacuumize processing, after handling 1～10h, obtain the poly butylene succinate prepolymer;
⑶ with the poly-sebacic acid 1 of step ⑴, the poly butylene succinate prepolymer of ammediol ester prepolymer and step ⑵ is by poly-sebacic acid 1, ammediol ester prepolymer: the mass ratio of poly butylene succinate prepolymer is that the ratio of 20:1～10:5 adds in the reactor, add catalyzer and oxidation inhibitor, at N
2Protection down; be warmed up to 160～200 ℃; carry out isothermal reaction 0.5～2h; under mechanical stirring, material is fully mixed; reaction system rises to 220～260 ℃ of condensation temperatures, strengthens vacuum tightness to the 0～100Pa of system simultaneously, behind polycondensation 3～10h; namely get poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester.
And, N among described step ⑴ and the ⑵
2N during protection
2Flow is 0.05～0.15m
3/ h.
And, poly-sebacic acid 1 among the described step ⑴, the general formula of ammediol ester prepolymer is as follows:
The general formula of poly butylene succinate prepolymer is as follows among the described step ⑵:
And, catalyzer is one or more in tin protochloride, stannous octoate, tin acetate, magnesium acetate, toluenesulphonic acids, polyphosphoric acid, dibutyltin dilaurate, toluenesulphonic acids, the positive butyl ester of metatitanic acid-4 among the described step ⑶, the add-on of catalyzer is poly-sebacic acid 1,0.1%～1% of ammediol ester prepolymer and poly butylene succinate prepolymer total mass; Oxidation inhibitor is phosphorous acid benzene two isodecyl esters, tricresyl phosphite (2 among the described step ⑶, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl phenyl) one or more in the ester, the add-on of oxidation inhibitor is poly-sebacic acid 1,0.1%～1% of ammediol ester prepolymer and poly butylene succinate prepolymer total mass.
And, N among the described step ⑶
2N during protection
2Flow is 0.05～0.15m
3/ h, stirring velocity is 100r/min.
And, described poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester also passes through following processing:
To gather sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester is used methanol extraction with the trichloromethane dissolving of heavily steaming, and takes out small-molecule substance, obtain the poly-sebacic acid 1 behind the purifying, ammediol ester-block-poly butylene succinate block polyester.
And the quality of described trichloromethane is poly-sebacic acid 1, and the 5-10 of ammediol ester-block-poly butylene succinate block polyester quality times, the mass ratio of trichloromethane and methyl alcohol is 1:10.
And, described poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester is in the aqueous solution of pH=4～6, and the degradation rate in 10 weeks reaches 25%～35%; In neutral aqueous solution, the degradation rate in 10 weeks reaches 5%～15%; In the aqueous solution of pH=8～10, the degradation rate in 10 weeks reaches 35%～50%; Be in 1～5mg/mL phosphate buffer soln in lipase concentration, the degradation rate in 10 weeks reaches 55%～75%, molecular weight and molecular weight 60%～80%.
The application in aspect making macromolecule material product of aforesaid poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester.
Advantage of the present invention and positively effect are:
1. the molecular weight ranges of polyester of the present invention is 10000～50000, its thermomechanical property and PBS are suitable, degradation property significantly improves, fusing point is higher than 100 ℃, better heat stability, have wideer processing space, can be applicable to make macromolecular material fields such as non-toxic degradable food product pack, degradable agricultural mulching, suture, have wide practical use.
2. the inventive method is at characteristics such as most aliphatic polyester fusing points are lower, low-melting polyester and dystectic polyester are carried out block polymerization, thereby obtain dystectic polyester, technology is simple, easy to control, can utilize existing conventional polyester poly-unit to carry out polymerization, simple to operate, be easy to the degradable polyester composite material that suitability for industrialized production has wideer processing space; Used monomer derives from biomass resource in the invention, and material source extensively and have a extensive future.
3. the inventive method is by dystectic poly-succinic acid-butanediol and low-melting poly-sebacic acid 1, ammediol carries out block modified, by different ratio proportionings and different modified conditions, structure, length, degree of crystallinity and the fusing point etc. of PBS molecular chain have been changed, obtained the type material that a series of thermomechanical properties and PBS are suitable, degradation rate significantly improves, significant in field of high polymer material processing and environmental protection field.
4. the inventive method adopts the mode that dystectic relatively PBS prepolymer and relative low-melting PPS prepolymer carry out block copolymerization, can obtain the higher poly-sebacic acid 1 of relative fusing point, ammediol ester (PPS)-block-poly butylene succinate (PBS) block polyester, fusing point all is higher than 100 ℃, and wideer processing space is arranged.
5. the inventive method is by optimizing the amount ratio of reactant, N
2Conditions such as the kind of flow, temperature of reaction, catalyzer and consumption, vacuum tightness and reaction times have improved the molecular weight of product greatly.
6. the inventive method is traditional melt-polycondensation, and is simple to operate, is convenient to promote, and the sebacic acid of selecting for use and 1, ammediol are the non-petroleum base product, can significantly reduce owing to smelt the outwards CO of discharging of oil
2Content not only can reduce production costs, but also environment protection is had active effect.
Description of drawings
Fig. 1 is PBS-block-PPS segmented copolymer infrared spectrogram among the present invention; Wherein, 1734cm
-1Be the absorption peak of C=O stretching vibration, 1167cm
-1Be the stretching vibration absorption peak of ester C-O, 2930cm
-1The place is C-H stretching vibration absorption peak, 3436cm
-1There is fainter hydroxyl charateristic avsorption band at the place, is the terminal hydroxy group in dibasic alcohol residual in the system or the polyester long-chain;
Fig. 2 is for PPS-block-PBS segmented copolymer among the present invention
1The H-NMR spectrogram; Wherein, δ=4.12ppm is the peak that of the methylene radical that links to each other with hydroxyl, δ=2.62ppm be link to each other methylene radical in the Succinic Acid structural unit with carbonyl go out the cutting edge of a knife or a sword position, δ=2.28ppm is the peak position that of methylene radical of linking to each other with carbonyl in the sebacic acid monomer, δ=1.95ppm is that propylene glycol intermediate sub methyl hydrogen goes out the cutting edge of a knife or a sword position, δ=1.6ppm place be on the sebacic acid with the carbonyl proton peak of two methylene radical of a carbon atom at interval, δ=1.71ppm be in the butyleneglycol unit methylene radical go out the cutting edge of a knife or a sword position, δ=1.3ppm is the peak that of middle 4 methylene radical of sebacic acid structural unit, illustrates that product is the PBS-block-PPS segmented copolymer;
Fig. 3 is crystallization curve in the DSC spectrogram of PBS-block-PPS segmented copolymer among the present invention, and Tc is 73 ℃;
Fig. 4 is melting curve in the DSC spectrogram of PBS-block-PPS segmented copolymer among the present invention, and melt temperature is 110.5 ℃;
Fig. 5 is the thermal weight loss spectrogram of PBS-block-PPS segmented copolymer among the present invention, and it begins weightless temperature and surpasses 300 ℃, and maximum weightless temperature is near 400 ℃, better heat stability.
Embodiment
The invention will be further described below by specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Biological degradable composite material of the present invention gathers sebacic acid 1, the preparation method of ammediol ester (PPS)-block-poly butylene succinate (PBS) block polyester (PPS-block-PBS segmented copolymer), at first take the mode of melt phase polycondensation to prepare the poly-sebacic acid 1 of lower molecular weight, 3 propylene glycol ester prepolymers and poly butylene succinate prepolymer, then above-mentioned two prepolymers are mixed, prepare poly-sebacic acid 1, ammediol ester (PPS)-block-poly butylene succinate (PBS) block polyester biodegradable composite by the mode of melt phase polycondensation.
In the polyester building-up process, because speed of response is slow and the equilibrium constant is less, must effectively control various physics and the chemical factor that influences reaction process, add fast response and impel reaction to move to the product direction.
The ratio of reaction monomers dibasic alcohol and diprotic acid is greater than 1 among the present invention, and scope is 1.5:1～1.1:1, guarantees hydroxy-end capped; Catalyst levels is less than 1% of the reactant quality among the present invention, and scope is 0.1%～1%; Described stabilizing agent dosage is less than 1% of the reactant quality, and scope is 0.1%～1%.
N among the present invention
2Protection, N
2Flow is unsuitable excessive, improves N otherwise influence vacuum tightness
2Flow range is 0.05～0.15m
3/ h, polycondensation phase is with 0.05m
3/ h is optimum.
A kind of poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester, its general formula is as follows:
Gather sebacic acid 1 as mentioned above, the preparation method of ammediol ester (PPS)-block-poly butylene succinate (PBS) block polyester (PPS-block-PBS), step is as follows:
(1) preparation of PBS prepolymer: take by weighing 11.8g(0.1mol respectively) Succinic Acid and 9.9g(0.11mol) butyleneglycol, add in three mouthfuls of round-bottomed flasks of 250mL, feed N
2, flow is 0.05m
3/ h is warming up to 160 ℃, after the complete fusion of monomer, carries out constant temperature stirring esterification 1h, and esterification end back (the general collecting amount of controlling generation water in the collection reaction process reaches 90% o'clock of theoretical value, thinks that esterification finishes) obtains the PBS performed polymer;
PBS prepolymer general formula is as follows:
Molecular weight ranges is 1000～10000.
(2) preparation of PPS prepolymer: take by weighing 20.2g(0.1mol respectively) sebacic acid and 8.36g(0.11mol) 1, ammediol adds in three mouthfuls of round-bottomed flasks of 250mL, feeds N
2, flow is 0.05m
3/ h, be warming up to 160 ℃, after the complete fusion of monomer, carry out constant temperature and stir esterification 2h, (the general collecting amount of controlling generation water in the collection reaction process reaches 90% o'clock of theoretical value in esterification end back, think that esterification finishes), in order to obtain the higher PPS performed polymer of molecular weight, taking to heat up vacuumizes further optimization process, system is warming up to 180 ℃ with the heat-up rate of 10 ℃/h, keep 5h down at 180 ℃, vacuum tightness is 50Pa, obtains the PPS performed polymer;
PPS prepolymer general formula is as follows:
(3) preparation of PPS-block-PBS segmented copolymer: get PBS prepolymer 90g and PPS prepolymer 10g respectively, add in the 500mL there-necked flask, add catalyzer tin protochloride 0.5g and oxidation inhibitor phosphorous acid benzene two isodecyl ester 1g, feed N
2, flow is 0.05m
3/ h, be warmed up to 180 ℃, under mechanical agitation, material is fully mixed, reaction 1h, system temperature rises to 240 ℃, 10 ℃/h of heat-up rate, at 240 ℃ of sustained reaction 3h, vacuum tightness is 50Pa, obtains PPS-block-PBS segmented copolymer crude product, and synthetic product is dissolved with the trichloromethane that heavily steamed, use methanol extraction, (concrete steps and principle are: at first PPS-block-PBS is put into an amount of chloroform solvent, 50 ℃ of lower magnetic forces stir 1h fully dissolves it, then this chloroformic solution is slowly poured in a large amount of methyl alcohol to remove small-molecule substance, be dissolved in the character that chloroform is insoluble to methyl alcohol by macromolecular material, obtain the macromole throw out, thereby small molecules removed), filtration drying obtains the PBS-block-PPS segmented copolymer behind the purifying;
Wherein, purifying is 10 times of product with the chloroform quality, and the mass ratio of chloroform and methyl alcohol is 1:10.
After testing, the fusing point of this PPS-block-PBS segmented copolymer is 110.5 ℃, and degree of crystallinity is 51%.
Embodiment 2
A kind of poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester, its general formula is as follows:
Gather sebacic acid 1 as mentioned above, the preparation method of ammediol ester (PPS)-block-poly butylene succinate (PBS) block polyester (PPS-block-PBS), step is as follows:
(1) preparation of PBS prepolymer: take by weighing 11.8g(0.1mol respectively) Succinic Acid and 10.8g(0.12mol) butyleneglycol, add in three mouthfuls of round-bottomed flasks of 250mL, feed N
2, flow is 0.08m
3/ h is warming up to 160 ℃, after the complete fusion of monomer, carries out constant temperature stirring esterification 2h, and esterification end back (the general collecting amount of controlling generation water in the collection reaction process reaches 90% o'clock of theoretical value, thinks that esterification finishes) obtains the PBS performed polymer;
PBS prepolymer general formula is as follows:
(2) preparation of PPS prepolymer: take by weighing 20.2g(0.1mol respectively) sebacic acid and 9.12g(0.12mol) 1, ammediol adds in three mouthfuls of round-bottomed flasks of 250mL, feeds N
2, flow is 0.05m
3/ h, be warming up to 160 ℃, after the complete fusion of monomer, carry out constant temperature and stir esterification 2h, esterification finishes the back, and (collecting amount of the water that generates in the general control collection reaction process reaches 90% o'clock of theoretical value, think that esterification finishes), in order to obtain the higher PPS performed polymer of molecular weight, taking to heat up vacuumizes further optimization process, system is warming up to 200 ℃ with the heat-up rate of 10 ℃/h, keep 5h down at 200 ℃, vacuum tightness is 50Pa, obtains the PPS performed polymer;
PPS prepolymer general formula is as follows:
(3) preparation of PPS-block-PBS segmented copolymer: get PBS prepolymer 95g and PPS prepolymer 5g respectively, add in the 500mL there-necked flask, adding composite catalyst 1g(tin protochloride and toluenesulphonic acids mass ratio is 2:1) and oxidation inhibitor tricresyl phosphite (2,4-di-tert-butyl phenyl) ester 1g feeds N
2, flow is 0.08m
3/ h, be warmed up to 180 ℃, under mechanical agitation, material is fully mixed, reaction 1h, then, system temperature rises to 240 ℃, 10 ℃/h of heat-up rate, at 240 ℃ of sustained reaction 5h, vacuum tightness is 50Pa, obtain PPS-block-PBS segmented copolymer crude product, synthetic product with the trichloromethane dissolving of heavily steaming, is used methanol extraction, and (concrete steps and principle are: at first PPS-block-PBS is put into an amount of chloroform solvent to remove small-molecule substance, 50 ℃ of lower magnetic forces stir 1h fully dissolves it, then this chloroformic solution is slowly poured in a large amount of methyl alcohol, be dissolved in the character that chloroform is insoluble to methyl alcohol by macromolecular material, obtain the macromole throw out, thereby small molecules is removed), filtration drying obtains the PPS-block-PBS segmented copolymer behind the purifying;
Wherein, purifying is 10 times of product with the chloroform quality, and the mass ratio of chloroform and methyl alcohol is 1:10.
After testing, 108.3 ℃ of the fusing points of this PBS-block-PPS segmented copolymer, degree of crystallinity is 47%.
A kind of poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester, its general formula is as follows:
Gather sebacic acid 1 as mentioned above, the preparation method of ammediol ester (PPS)-block-poly butylene succinate (PBS) block polyester (PPS-block-PBS), step is as follows:
(1) preparation of PBS prepolymer: take by weighing 11.8g(0.1mol respectively) Succinic Acid and 11.7g(0.13mol) butyleneglycol, add in three mouthfuls of round-bottomed flasks of 250mL, feed N
2, flow is 0.1m
3/ h, be warming up to 160 ℃ to the complete fusion of monomer, carry out constant temperature stirring esterification 3h, esterification finishes the back, and (collecting amount of the water that generates in the general control collection reaction process reaches 90% o'clock of theoretical value, think that esterification finishes), obtain the PBS performed polymer;
PBS prepolymer general formula is as follows:
(2) preparation of PPS prepolymer: take by weighing 20.2g(0.1mol respectively) sebacic acid and 9.88g(0.13mol) 1, ammediol adds in three mouthfuls of round-bottomed flasks of 250mL, feeds N
2, flow is 0.05m
3/ h, be warming up to 160 ℃, after the complete fusion of monomer, carry out constant temperature and stir esterification 2h, esterification finishes the back, and (collecting amount of the water that generates in the general control collection reaction process reaches 90% o'clock of theoretical value, think that esterification finishes), in order to obtain the higher PPS performed polymer of molecular weight, taking to heat up vacuumizes further optimization process, system is warming up to 190 ℃ with the heat-up rate of 10 ℃/h, keep 5h down at 190 ℃, vacuum tightness is 50Pa, obtains the PPS performed polymer;
PPS prepolymer general formula is as follows:
(3) preparation of PPS-block-PBS segmented copolymer: get PBS prepolymer 85g and PPS prepolymer 15g respectively, add in the 500mL there-necked flask, the mass ratio that adds the positive butyl ester of composite catalyst 0.5g(metatitanic acid-4 and dibutyltin dilaurate is 2:1,) and oxidation inhibitor 1g(phosphorous acid benzene two isodecyl esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) mass ratio of ester is 1:1), feed N
2, flow is 0.05m
3/ h, be warmed up to 180 ℃, under mechanical agitation, material is fully mixed, reaction 1h, system temperature rises to 240 ℃ then, 10 ℃/h of heat-up rate, at 260 ℃ of sustained reaction 3h, vacuum tightness is 50Pa, obtains PPS-block-PBS segmented copolymer crude product, and synthetic product is dissolved with the trichloromethane that heavily steamed, use methanol extraction, (concrete steps and principle are: at first PPS-block-PBS is put into an amount of chloroform solvent, 50 ℃ of lower magnetic forces stir 1h fully dissolves it, then this chloroformic solution is slowly poured in a large amount of methyl alcohol to remove small-molecule substance, be dissolved in the character that chloroform is insoluble to methyl alcohol by macromolecular material, obtain the macromole throw out, thereby small molecules removed), filtration drying obtains the PBS-block-PBS segmented copolymer behind the purifying;
Wherein, purifying is 10 times of product with the chloroform quality, and the mass ratio of chloroform and methyl alcohol is 1:10.
After testing, 106.5 ℃ of the fusing points of this PBS-block-PPS segmented copolymer, degree of crystallinity is 42.2%.
Embodiment 4
A kind of poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester, its general formula is as follows:
Gather sebacic acid 1 as mentioned above, the preparation method of ammediol ester (PPS)-block-poly butylene succinate (PBS) block polyester (PPS-block-PBS), step is as follows:
(1) preparation of PBS prepolymer: take by weighing 11.8g(0.1mol respectively) Succinic Acid and 12.6g(0.14mol) butyleneglycol, add in three mouthfuls of round-bottomed flasks of 250mL, feed N
2, flow is 0.1m
3/ h is warming up to 160 ℃, after the complete fusion of monomer, carries out constant temperature stirring esterification 2h, and esterification end back (the general collecting amount of controlling generation water in the collection reaction process reaches 90% o'clock of theoretical value, thinks that esterification finishes) obtains the PBS performed polymer;
PBS prepolymer general formula is as follows:
(2) preparation of PPS prepolymer: take by weighing 20.2g(0.1mol respectively) sebacic acid and 10.64g(0.14mol) 1, ammediol adds in three mouthfuls of round-bottomed flasks of 250mL, feeds N
2, flow is 0.05m
3/ h, be warming up to 160 ℃, after the complete fusion of monomer, carry out constant temperature and stir esterification 2h, (collecting amount of the water that generates in the general control collection reaction process reaches 90% o'clock of theoretical value to react the end back, think that esterification finishes), in order to obtain the higher PPS performed polymer of molecular weight, taking to heat up vacuumizes further optimization process, system is warming up to 200 ℃ with the heat-up rate of 10 ℃/h, keep 5h down at 200 ℃, vacuum tightness is 50Pa, obtains the PPS performed polymer;
PPS prepolymer general formula is as follows:
(3) preparation of PPS-block-PBS segmented copolymer: get PBS prepolymer 80g and PPS prepolymer 20g respectively, add in the 500mL there-necked flask, add catalyzer toluenesulphonic acids 0.5g and oxidation inhibitor 1g(tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester and tricresyl phosphite (2,4-di-tert-butyl phenyl) mass ratio of ester is 2:1), feed N
2, flow is 0.05m
3/ h, be warmed up to 180 ℃, be that material fully mixes under mechanical agitation, reaction times 1h, system temperature rises to 240 ℃ then, 10 ℃/h of heat-up rate, at 260 ℃ of sustained reaction 5h, vacuum tightness is 50Pa, obtains PPS-block-PBS segmented copolymer crude product, and synthetic product is dissolved with the trichloromethane that heavily steamed, use methanol extraction, (concrete steps and principle are: at first PPS-block-PBS is put into an amount of chloroform solvent, 50 ℃ of lower magnetic forces stir 1h fully dissolves it, then this chloroformic solution is slowly poured in a large amount of methyl alcohol to remove small-molecule substance, be dissolved in the character that chloroform is insoluble to methyl alcohol by macromolecular material, obtain the macromole throw out, thereby small molecules removed), filtration drying obtains the PPS-block-PBS segmented copolymer behind the purifying;
Wherein, purifying is 10 times of product with the chloroform quality, and the mass ratio of chloroform and methyl alcohol is 1:10.
After testing, 108.7 ℃ of the fusing points of this PBS-block-PPS segmented copolymer, degree of crystallinity is 39.2%.
Embodiment 5
A kind of poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester, its general formula is as follows:
, molecular weight ranges is 10000～50000.
Gather sebacic acid 1 as mentioned above, the preparation method of ammediol ester (PPS)-block-poly butylene succinate (PBS) block polyester (PPS-block-PBS), step is as follows:
(1) preparation of PBS prepolymer: take by weighing 11.8g(0.1mol respectively) Succinic Acid and 12.15g(0.15mol) butyleneglycol, add in three mouthfuls of round-bottomed flasks of 250mL, feed N
2, flow is 0.05m
3/ h is warming up to 160 ℃, after the complete fusion of monomer, carry out constant temperature and stir esterification 2h, esterification finishes back (collecting amount of the water that generates in the general control collection reaction process reaches 90% o'clock of theoretical value, thinks that esterification finishes), obtains the PBS performed polymer;
PBS prepolymer general formula is as follows:
Molecular weight ranges is 1000～10000.
(2) preparation of PPS prepolymer: take by weighing 20.2g(0.1mol respectively) sebacic acid and 11.4g(0.15mol) 1, ammediol adds in three mouthfuls of round-bottomed flasks of 250mL, feeds N
2, flow is 0.05m
3/ h, be warming up to 160 ℃, after the complete fusion of monomer, carry out constant temperature and stir esterification 2h, (the general collecting amount of controlling generation water in the collection reaction process reaches 90% o'clock of theoretical value in esterification end back, think that esterification finishes), in order to obtain the higher PPS performed polymer of molecular weight, taking to heat up vacuumizes further optimization process, system is warming up to 180 ℃ with the heat-up rate of 10 ℃/h, keep 5h down at 180 ℃, vacuum tightness is 50Pa, obtains the PPS performed polymer;
PPS prepolymer general formula is as follows:
(3) preparation of PPS-block-PBS segmented copolymer: get PBS prepolymer 75g and PPS prepolymer 25g respectively, add in the 500mL there-necked flask, add the positive butyl ester 0.5g of catalyzer metatitanic acid-4 and oxidation inhibitor tricresyl phosphite (2,4-di-tert-butyl phenyl) ester 1g, feed N
2, flow is 0.05m
3/ h, be warmed up to 180 ℃, be that material fully mixes under the mechanical agitation, reaction 1h, system rises to 240 ℃, 10 ℃/h of heat-up rate, at 240 ℃ of sustained reaction 3h, vacuum tightness is 50Pa, obtains PPS-block-PPS segmented copolymer crude product, and synthetic product is dissolved with the trichloromethane that heavily steamed, use methanol extraction then, (concrete steps and principle are: at first PPS-block-PBS is put into an amount of chloroform solvent, 50 ℃ of lower magnetic forces stir 1h fully dissolves it, then this chloroformic solution is slowly poured in a large amount of methyl alcohol to remove small-molecule substance, be dissolved in the character that chloroform is insoluble to methyl alcohol by macromolecular material, obtain the macromole throw out, thereby small molecules removed), filtration drying obtains the PBS-block-PPS segmented copolymer behind the purifying;
Wherein, purifying is 10 times of product with the chloroform quality, and the mass ratio of chloroform and methyl alcohol is 1:10.
After testing, 103.5 ℃ of the fusing points of this PBS-block-PPS segmented copolymer, degree of crystallinity is 44.2%.
Poly-sebacic acid 1 among the present invention, the detection of ammediol ester-block-poly butylene succinate block polyester:
After testing, the Tc of this PBS-block-PPS segmented copolymer is 73 ℃ of (see figure 3)s, and melt temperature is 110.5 ℃ of (see figure 4)s, and the fusing point of this segmented copolymer is higher than 100 ℃, and wideer processing space is arranged;
Its thermal weight loss spectrogram (see figure 5) shows that it begins weightless temperature and surpasses 300 ℃, and maximum weightless temperature is near 400 ℃, better heat stability.
Detect through degradation rate, this PPS-block-PBS segmented copolymer is compared with the single polymers of PBS, and more superior degradation property is arranged: in the aqueous solution of pH=4～6, the degradation rate in 10 weeks can reach 25%～35%; In neutral aqueous solution, the degradation rate in 10 weeks can reach 5%～15%; In the aqueous solution of pH=8～10, the degradation rate in 10 weeks can reach 35%～50%; Be in 1～5mg/mL phosphate buffer soln in lipase concentration, the degradation rate in 10 weeks can reach 55%～75%, molecular weight and molecular weight 60%～80%.
The fusing point of PPS-block-PBS multipolymer of the present invention all is higher than 100 ℃, and wideer processing space is arranged.To sum up, the present invention can be applied to make in the macromolecular material goods fields such as degradable food product pack, degradable agricultural mulching, suture.
Claims (10)
1. poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester is characterized in that: this poly-sebacic acid 1, the general formula of ammediol ester-block-poly butylene succinate block polyester is as follows:
, molecular weight ranges is 10000～50000.
2. poly-sebacic acid 1 as claimed in claim 1, the preparation method of ammediol ester-block-poly butylene succinate block polyester, it is characterized in that: step is as follows:
⑴ gather sebacic acid 1, the preparation of ammediol ester prepolymer: with Succinic Acid and butyleneglycol in Succinic Acid: the amount of substance of butyleneglycol is than placing reactor for the ratio of 1:1～1:1.5, at N
2Protection is warming up to 160～180 ℃ down, after the complete fusion of monomer, carries out constant temperature and stirs esterification 1～5h, after reaction finishes, obtains poly-sebacic acid 1, ammediol ester prepolymer;
⑵ the preparation of poly butylene succinate prepolymer: with sebacic acid and 1, ammediol is pressed sebacic acid: 1, and the amount of substance of ammediol is than placing reactor for the ratio of 1:1～1:1.5, at N
2Protection down, be warming up to 160～180 ℃, after the complete fusion of monomer, carry out constant temperature and stir esterification, esterification 1～5h, after esterification finished, 160～200 ℃, vacuum ranges were to heat up under the condition of 50～500Pa to vacuumize processing, after handling 1～10h, obtain the poly butylene succinate prepolymer;
⑶ with the poly-sebacic acid 1 of step ⑴, the poly butylene succinate prepolymer of ammediol ester prepolymer and step ⑵ is by poly-sebacic acid 1, ammediol ester prepolymer: the mass ratio of poly butylene succinate prepolymer is that the ratio of 20:1～10:5 adds in the reactor, add catalyzer and oxidation inhibitor, at N
2Protection down; be warmed up to 160～200 ℃; carry out isothermal reaction 0.5～2h; under mechanical stirring, material is fully mixed; reaction system rises to 220～260 ℃ of condensation temperatures, strengthens vacuum tightness to the 0～100Pa of system simultaneously, behind polycondensation 3～10h; namely get poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester.
3. poly-sebacic acid 1 according to claim 2, the preparation method of ammediol ester-block-poly butylene succinate block polyester is characterized in that: N among described step ⑴ and the ⑵
2N during protection
2Flow is 0.05～0.15m
3/ h.
4. poly-sebacic acid 1 according to claim 2, the preparation method of ammediol ester-block-poly butylene succinate block polyester is characterized in that: poly-sebacic acid 1 among the described step ⑴, the general formula of ammediol ester prepolymer is as follows:
The general formula of poly butylene succinate prepolymer is as follows among the described step ⑵:
5. poly-sebacic acid 1 according to claim 2, the preparation method of ammediol ester-block-poly butylene succinate block polyester, it is characterized in that: catalyzer is one or more in tin protochloride, stannous octoate, tin acetate, magnesium acetate, toluenesulphonic acids, polyphosphoric acid, dibutyltin dilaurate, toluenesulphonic acids, the positive butyl ester of metatitanic acid-4 among the described step ⑶, the add-on of catalyzer is poly-sebacic acid 1,0.1%～1% of ammediol ester prepolymer and poly butylene succinate prepolymer total mass; Oxidation inhibitor is phosphorous acid benzene two isodecyl esters, tricresyl phosphite (2 among the described step ⑶, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl phenyl) one or more in the ester, the add-on of oxidation inhibitor is poly-sebacic acid 1,0.1%～1% of ammediol ester prepolymer and poly butylene succinate prepolymer total mass.
6. poly-sebacic acid 1 according to claim 2, the preparation method of ammediol ester-block-poly butylene succinate block polyester is characterized in that: N among the described step ⑶
2N during protection
2Flow is 0.05～0.15m
3/ h, stirring velocity is 100r/min.
7. according to each described poly-sebacic acid 1 of claim 2 to 6, the preparation method of ammediol ester-block-poly butylene succinate block polyester, it is characterized in that: described poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester also passes through following processing:
To gather sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester is used methanol extraction with the trichloromethane dissolving of heavily steaming, and takes out small-molecule substance, obtain the poly-sebacic acid 1 behind the purifying, ammediol ester-block-poly butylene succinate block polyester.
8. poly-sebacic acid 1 according to claim 7, the preparation method of ammediol ester-block-poly butylene succinate block polyester, it is characterized in that: the quality of described trichloromethane is poly-sebacic acid 1, the 5-10 of ammediol ester-block-poly butylene succinate block polyester quality times, the mass ratio of trichloromethane and methyl alcohol is 1:10.
9. poly-sebacic acid 1 according to claim 7, the preparation method of ammediol ester-block-poly butylene succinate block polyester, it is characterized in that: described poly-sebacic acid 1, ammediol ester-block-poly butylene succinate block polyester is in the aqueous solution of pH=4～6, and the degradation rate in 10 weeks reaches 25%～35%; In neutral aqueous solution, the degradation rate in 10 weeks reaches 5%～15%; In the aqueous solution of pH=8～10, the degradation rate in 10 weeks reaches 35%～50%; Be in 1～5mg/mL phosphate buffer soln in lipase concentration, the degradation rate in 10 weeks reaches 55%～75%, molecular weight and molecular weight 60%～80%.
10. the application in aspect making macromolecule material product of poly-sebacic acid 1 as claimed in claim 1, ammediol ester-block-poly butylene succinate block polyester.
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| CN101649045A (en) * | 2008-08-11 | 2010-02-17 | 中国科学院化学研究所 | Biodegradable polyester-polyester segmented copolymer, preparation method and application thereof |
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| GIORGIO MONTAUDO ET AL: ""Synthesis and enzymatic degradation of aliphatic copolyesters"", 《POLYMER DEGRADATION AND STABILITY》 * |
| S.S. UMARE ET AL: ""Synthesis, characterization and biodegradable studies of 1,3-propanediol based polyesters"", 《POLYMER DEGRADATION AND STABILITY》 * |
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