CN1233686C - Process for preparing fatty polyester with variable degradative speed rate and preparation proces sof product thereof - Google Patents
Process for preparing fatty polyester with variable degradative speed rate and preparation proces sof product thereof Download PDFInfo
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- CN1233686C CN1233686C CN 200410021996 CN200410021996A CN1233686C CN 1233686 C CN1233686 C CN 1233686C CN 200410021996 CN200410021996 CN 200410021996 CN 200410021996 A CN200410021996 A CN 200410021996A CN 1233686 C CN1233686 C CN 1233686C
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- aliphatic polyesters
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- lewis acid
- degradation rates
- acid catalyst
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- 229920000728 polyester Polymers 0.000 title claims 2
- 238000002360 preparation method Methods 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 2
- 230000003413 degradative effect Effects 0.000 title 1
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 59
- 230000015556 catabolic process Effects 0.000 claims abstract description 42
- 238000006731 degradation reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 31
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 26
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 238000012545 processing Methods 0.000 claims abstract description 6
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims description 44
- 238000003490 calendering Methods 0.000 claims description 16
- 238000005469 granulation Methods 0.000 claims description 16
- 230000003179 granulation Effects 0.000 claims description 16
- 238000001746 injection moulding Methods 0.000 claims description 16
- 238000009987 spinning Methods 0.000 claims description 16
- -1 polybutylene succinate Polymers 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- 229920002961 polybutylene succinate Polymers 0.000 claims description 10
- 239000004631 polybutylene succinate Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 238000000071 blow moulding Methods 0.000 claims 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims 2
- 238000010309 melting process Methods 0.000 claims 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 238000007664 blowing Methods 0.000 description 14
- 229920003023 plastic Polymers 0.000 description 14
- 239000004033 plastic Substances 0.000 description 14
- 239000000155 melt Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229920002463 poly(p-dioxanone) polymer Polymers 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical group FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003937 drug carrier Substances 0.000 description 3
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000941 bile Anatomy 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical class [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
Abstract
本发明涉及一种制备具有不同降解速率脂肪族聚酯或其制品的方法，其特征是在脂肪族聚酯的聚合过程中或/和脂肪族聚酯与其制品的加工过程中，加入重量百分比为0.1～6%的路易斯酸类催化剂。本发明方法简便易行，所用路易斯酸类催化剂添加量少，降解促进作用显著，对脂肪族聚酯本身的生物相容性和可生物降解性无任何影响，可根据实际需要，通过添加不同量的催化剂，来调控脂肪族聚酯的降解速率，以满足不同的使用要求，尤其是可扩大聚ε-己内酯、聚L-丙交酯等降解速率较慢的脂肪族聚酯的应用范围。The present invention relates to a method for preparing aliphatic polyesters with different degradation rates or their products, which is characterized in that during the polymerization of aliphatic polyesters or/and during the processing of aliphatic polyesters and their products, the weight percentage of 0.1-6% Lewis acid catalyst. The method of the present invention is simple and easy to implement, the amount of Lewis acid catalyst added is small, the degradation promotion effect is remarkable, and the biocompatibility and biodegradability of the aliphatic polyester itself have no effect. According to actual needs, by adding different amounts catalysts to regulate the degradation rate of aliphatic polyesters to meet different application requirements, especially to expand the application range of aliphatic polyesters with slow degradation rates such as polyε-caprolactone and poly-L-lactide .
Description
One, technical field
The invention belongs to controlling polymers degradation technique field, be specifically related to the method that a kind of preparation has different degradation rate aliphatic polyesters or its goods.
Two, background technology
Good biocompatibility that aliphatic polyester itself has and biodegradable, especially biodegradable make it to be widely used as bio-medical material and environment-friendly material.Representational biodegradable aliphatic polyester mainly contains: poly-epsilon-caprolactone (PCL), PPDO (PPDO), poly-glycollide (PGA), polylactide (PLA), poly butylene succinate (PBS), polyethylene glycol succinate (PES), poly adipate succinic acid ester (PBA) and poly--3-hydroxyl butyl ester [P (3-HB)] etc.Difference on the The Nomenclature Composition and Structure of Complexes of these aliphatic polyesters has been given different separately biodegradable performance and purposes.Very fast as poly-glycollide degradation in vivo speed, suitable operate suture line and slow releasing pharmaceutical carrier.The degradation speed of polylactide and poly-L-rac-Lactide is slower, suitable do material implanted, slower because of degradation speed if, only be applicable to depot drug product at present for fugitive medicine as the slow releasing pharmaceutical carrier, be difficult for absorbing in vivo and be restricted; As it is used as environmentally conscious materials,, after can't adapting to these materials and be used to complete, their degradation speed needs the requirement of degraded rapidly as agricultural mulching, food bag, refuse bag etc.Therefore, expand the purposes of various aliphatic polyesters, seek to make its degradation property to obtain the approach of effectively control and adjusting, be the important topic of macromolecular material researcher research.
At present, according to bibliographical information, the degradation property of control and adjusting aliphatic polyester adopts the method for copolymerization that it is carried out modification usually.This method is the composition by the control multipolymer, and character such as the wetting ability of change polymkeric substance, crystallinity satisfy some service requirements.After glycollide (GA) and rac-Lactide (LA) copolymerization, can make degradation speed improve 10 times than polylactide homopolymer, and can be by changing the ratio of component of glycollide and rac-Lactide, reach the effect (J.Biomed.Mater.Res. of the degradation rate of regulating multipolymer effectively, 1977,11,711-719; Polymer, 1981,22,494-498; U.S.4,011,312; U.S.3,982,543.).And for example poly-epsilon-caprolactone is a slower kind of typical degraded in the aliphatic polyester, it also can adopt various biocompatible monomer such as glycollide (GA), rac-Lactide (LA) and polyoxyethylene glycol (PEG) etc. and 6-caprolactone (ε-CL) copolymerization, improve the degradation property of poly-epsilon-caprolactone, thereby obtain to have the macromolecular material of different degradation rates, to adapt to the different pharmaceutical carrier in the intravital absorption requirement of people, make good release of poly-epsilon-caprolactone and biodegradable realize to regulate control (J.Polym.Sci.Part A:Polym.Chem., 2002,40,544-554; Contemp.Topics in Polym.Sci., 1977,2,251-289; The functional polymer journal, 2002,14 (1), 67-71.).The degradation behavior of polymkeric substance in environment such as bile, blood plasma, pancreas suspension that poly-epsilon-caprolactone and rac-Lactide and 6-caprolactone monomer are obtained by the copolymerization of different mole proportioning, compare research, the result shows that the degradation rate of multipolymer is significantly higher than poly-epsilon-caprolactone homopolymer (The Fourth Military Medical University's journal, 2001,22 (7), 604-608.).
Though the modification by copolymerization method can reach the purpose of regulation and control aliphatic polyester degradation rate, this method is also inconvenient in actually operating.Because modified monomer must be introduced when polymer manufacture, in case after polymerization was finished, the degradation rate of polymkeric substance just was difficult to change according to actual needs again.In addition, multipolymer is different from homopolymer after all on physics, chemical property, can bring some detrimentally affects to application sometimes even also.Though have excellent biological compatibility, do not possess biodegradable such as polyoxyethylene glycol (PEG), therefore, the aliphatic polyester copolymer that contains the polyoxyethylene glycol segment just can not be degraded fully, and its application will inevitably be subjected to certain limitation.
Three, summary of the invention
The objective of the invention is the defective that exists at existing modification by copolymerization method, provide a kind of be different from modification by copolymerization, preparation has the method for different degradation rate aliphatic polyesters or its goods.
Preparation provided by the invention has the method for different degradation rate aliphatic polyesters or its goods, it is characterized in that in the polymerization process of aliphatic polyester or/and in the course of processing of aliphatic polyester and its goods that the adding weight percent is 0.1～6% lewis acid catalyst.
Wherein aliphatic polyester is any in poly-epsilon-caprolactone, poly-L-rac-Lactide, PPDO, poly butylene succinate, the poly adipate succinic acid ester.
Lewis acid catalyst is selected BF for use
3, AlCl
3, SnCl
4, ZnCl
2, TiCl
4, TiBr
4In any.
Preparation has different degradation rate aliphatic polyesters in the polymerization process that is chosen in aliphatic polyester, and its lewis acid catalyst is to add with monomer, initiator, and its polymerization process condition is identical with corresponding conventional polymerization process condition.Initiator uses Organoalkyl or alkoxide compound usually, as stannous octoate, triethyl aluminum, aluminum isopropylate, three lanthanum isopropoxides, tetrabutyl titanate etc.
In the melt-processed process that is chosen in aliphatic polyester and its goods; preparation has different degradation rate aliphatic polyesters; must be earlier with lewis acid catalyst and aliphatic polyester premix 3～8 minutes; put into then mixing roll or single screw extrusion machine or twin screw extruder routinely processing condition carry out melt blending, granulation or directly be processed into corresponding articles through blowing, plastic uptake, injection moulding, spinning, calendering technology.
In the solution course of processing that is chosen in aliphatic polyester, preparation has different degradation rate aliphatic polyesters, then must be with aliphatic polyester by 3～5% weight percent concentration, after the corresponding solvent dissolving, lewis acid catalyst is added wherein, and mixed at normal temperatures 5～24 hours, get final product except that desolvating then.Heated or constant-temperature evaporation except that the method for desolvating both can adopt, also can adopt the removal method that vacuumizes.
If also need increase the degradation rate of the aliphatic polyester that in above-mentioned polymerization process, has prepared, can be respectively by in the process of melt-processed or solution processing, the lewis acid catalyst that continues the interpolation sufficient quantity reaches.
The present invention has following advantage:
1,, the biocompatibility and the biodegradable of aliphatic polyester itself had no effect because the present invention controls and regulate the degradation rate of aliphatic polyester by adding lewis acid catalyst, and the degraded promoter action that it shows belongs to chemical degradation.
2, because the present invention both can be in the polymerization process of aliphatic polyester or in the course of processing of aliphatic polyester and its goods, prepare and have different degradation rate aliphatic polyesters by adding lewis acid catalyst, can also be again post-treatment process by aliphatic polyester and its goods, the aliphatic polyester of certain degradation rate is finished, has been had in continuation to polymerization, change its degradation rate according to actual needs, thereby can overcome the shortcoming of existing modification by copolymerization method in actually operating inconvenience.
3, the used lewis acid catalyst addition of the present invention is few, the degraded promoter action is remarkable, can be according to actual needs, add the catalyzer of different amounts, regulate and control the degradation rate of aliphatic polyester, to satisfy different service requirementss, especially can enlarge the range of application of the slower aliphatic polyester of degradation rates such as poly-epsilon-caprolactone, poly-L-rac-Lactide.
4, no matter the used degraded promoter action that lewis acid catalyst showed of the present invention is by polycoordination, and still the aliphatic polyester that obtains by contract and polymerization etc. all has general character, is not subjected to the restriction of aliphatic polyester polymerization process.
Four, embodiment
Provide embodiment below so that the invention will be further described; but be pointed out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art of this area foregoing according to the present invention still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes.
Embodiment 1
In 4 polymerizing pipes, add respectively earlier the 10mL 6-caprolactone and with the mol ratio of 6-caprolactone be 1: 1000 stannous octoate, add concentration more respectively and be 46.8%, density is the boron trifluoride diethyl etherate (BF of 1.13 g/mL
3OEt
2) solution 0,5,25,50 μ L, put into oil bath then, under nitrogen or argon shield, in 110 ℃ of polymerization 48h.After polymerization is finished, from polymerizing pipe, take out polymkeric substance, be placed in the air.
With the above-mentioned poly-epsilon-caprolactone that obtains, after placing different time, take a sample, make solvent with benzene, come the molecular weight of monitoring polymer to change with Ubbelohde viscometer in 30 ℃ of limiting viscosities [η] of surveying polymkeric substance.The aerial degraded situation of 4 polymkeric substance such as the following table of gained:
| BF 3·OEt 2Add-on (μ L) | 0 | 5 | 25 | 50 |
| Polymkeric substance initial [η] | 1.02 | 0.85 | 0.48 | 0.37 |
| Place after 7 days [η] | 1.02 | 0.81 | 0.43 | 0.32 |
| Place after 14 days [η] | 1.02 | 0.75 | 0.40 | 0.26 |
| Place after 35 days [η] | 1.02 | 0.71 | 0.31 | 0.21 |
Embodiment 2
Take by weighing initial intrinsic viscosity [η] and be each 1.0g of poly-epsilon-caprolactone of 1.02 in 4 band plug Erlenmeyer flasks, add benzene 20mL, after treating that it dissolves fully, under the normal temperature, add respectively with microsyringe that concentration is 46.8%, density is boron trifluoride ether solution 0,10,20, the 50 μ L of 1.13g/mL, magnetic agitation is mixed 24h, changes above-mentioned solution over to 4 culture dish, in exsiccator, vacuumize to remove and desolvate, get final product 40 ℃ of vacuum-drying to constant weights at last.
With the above-mentioned poly-epsilon-caprolactone that obtains, record limiting viscosity [η] with the test condition of embodiment 1 and be respectively 1.02,0.85,0.64,0.26.
Embodiment 3
Take by weighing with tetrahydrofuran (THF) and make solvent, polystyrene is made standard, utilizing gel permeation chromatography to survey its weight-average molecular weight Mw is 42144, number-average molecular weight Mn is that 12715 poly-epsilon-caprolactone 1.0g is in a band plug Erlenmeyer flask, add benzene 20mL, after treating that it dissolves fully, under the normal temperature, add with microsyringe that concentration is 46.8%, density is the boron trifluoride ether solution 100 μ L of 1.13g/mL, magnetic agitation 24h, change this solution over to a culture dish, in exsiccator, vacuumize to remove and desolvate, get final product 40 ℃ of vacuum-drying to constant weights at last.
With the above-mentioned poly-epsilon-caprolactone that obtains, survey its weight-average molecular weight Mw with gel permeation chromatography and drop to 8252, number-average molecular weight Mn drops to 2520.
Embodiment 4
Elder generation is 1.02 97 parts of granular poly-epsilon-caprolactones, AlCl with initial intrinsic viscosity [η]
33 parts of pre-mixing 5min in high-speed mixer; then the mixture after the pre-mixing is put into twin screw extruder; 80～120 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained poly-epsilon-caprolactone records limiting viscosity [η] with the test condition of embodiment 1 and drops to 0.54.
Embodiment 5
Elder generation is 1.02 97 parts of granular poly-epsilon-caprolactones, ZnCl with initial intrinsic viscosity [η]
23 parts of pre-mixing 3min in high-speed mixer; then the mixture after the pre-mixing is put into twin screw extruder; 80～120 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained poly-epsilon-caprolactone records limiting viscosity [η] with the test condition of embodiment 1 and drops to 0.60.
Embodiment 6
Elder generation is 1.02 97 parts of granular poly-epsilon-caprolactones, SnCl with initial intrinsic viscosity [η]
43 parts of pre-mixing 6min in high-speed mixer; then the mixture after the pre-mixing is put into twin screw extruder; 80～120 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained poly-epsilon-caprolactone records limiting viscosity [η] with the test condition of embodiment 1 and drops to 0.56.
Embodiment 7
Elder generation is 1.02 97 parts of granular poly-epsilon-caprolactones, TiCl with initial intrinsic viscosity [η]
43 parts of pre-mixing 8min in high-speed mixer; then the mixture after the pre-mixing is put into twin screw extruder; 80～120 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained poly-epsilon-caprolactone records limiting viscosity [η] with the test condition of embodiment 1 and drops to 0.64.
Embodiment 8
Elder generation is 1.02 97 parts of granular poly-epsilon-caprolactones, TiBr with initial intrinsic viscosity [η]
43 parts of pre-mixing 5min in high-speed mixer; then the mixture after the pre-mixing is put into twin screw extruder; 80～120 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained poly-epsilon-caprolactone records limiting viscosity [η] with the test condition of embodiment 1 and drops to 0.59.
Embodiment 9
Elder generation is 2.10 97 parts of granular poly-L-rac-Lactides, AlCl with initial intrinsic viscosity [η]
33 parts of pre-mixing 5min in high-speed mixer; then the mixture after the pre-mixing is added in the twin screw extruder; 170～220 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The poly-L-rac-Lactide of gained records limiting viscosity [η] with Ubbelohde viscometer in 25 ℃ and drops to 1.13 with the chloroform give solvent.
Embodiment 10
Elder generation is 2.10 98 parts of granular poly-L-rac-Lactides, AlCl with initial intrinsic viscosity [η]
32 parts of pre-mixing 3min in high-speed mixer; then the mixture after the pre-mixing is added in the twin screw extruder; 170～220 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The poly-L-rac-Lactide of gained records limiting viscosity [η] with the test condition of embodiment 9 and drops to 1.41.
Embodiment 11
Take by weighing initial intrinsic viscosity [η] and be each 1.0g of poly butylene succinate of 0.64 in 4 band plug Erlenmeyer flasks, add chloroform 20mL, after treating that it dissolves fully, under the normal temperature, add respectively with microsyringe that concentration is 46.8%, density is boron trifluoride ether solution 0,10,20, the 50 μ L of 1.13 g/mL, magnetic agitation 10h changes above-mentioned solution over to 4 culture dish, in exsiccator, vacuumize to remove and desolvate, get final product 40 ℃ of vacuum-drying to constant weights at last.
With the above-mentioned poly butylene succinate that obtains,, survey limiting viscosity [η] with Ubbelohde viscometer in 20 ℃ and be respectively 0.64,0.56,0.41,0.28 with the chloroform give solvent.
Embodiment 12
Elder generation is 0.92 98 parts of granular poly butylene succinates, ZnCl with initial intrinsic viscosity [η]
22 parts of pre-mixing 6min in high-speed mixer; then the mixture after the pre-mixing is added in the twin screw extruder; 180～240 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained poly butylene succinate records limiting viscosity [η] with the test condition of embodiment 11 and drops to 0.61.
Embodiment 13
Elder generation is 0.92 98 parts of granular poly butylene succinates, AlCl with initial intrinsic viscosity [η]
32 parts of pre-mixing 4min in high-speed mixer; then the mixture after the pre-mixing is added in the twin screw extruder; 180～240 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained poly butylene succinate records limiting viscosity [η] with the test condition of embodiment 11 and drops to 0.50.
Embodiment 14
Elder generation is 0.84 98 parts of granular poly adipate succinic acid esters, AlCl with initial intrinsic viscosity [η]
32 parts of pre-mixing 5min in high-speed mixer; then the mixture after the pre-mixing is added in the twin screw extruder; 180～240 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained poly adipate succinic acid ester records limiting viscosity [η] with the test condition of embodiment 11 and drops to 0.46.
Embodiment 15
Elder generation is 0.84 98 parts of granular poly adipate succinic acid esters, ZnCl with initial intrinsic viscosity [η]
22 parts of pre-mixing 8min in high-speed mixer; then the mixture after the pre-mixing is added in the twin screw extruder; 180～240 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained poly adipate succinic acid ester records limiting viscosity [η] with the test condition of embodiment 11 and drops to 0.51.
Embodiment 16
Take by weighing initial intrinsic viscosity [η] and be each 1.0g of PPDO of 0.31 in 4 band plug Erlenmeyer flasks, add 1,1,2,2-tetrachloroethane 20mL, heating is dissolved it fully, is cooled to room temperature again, adds respectively with microsyringe that concentration is 46.8%, density is boron trifluoride ether solution 0,10,20, the 50 μ L of 1.13g/mL, magnetic agitation 16h, change above-mentioned solution over to 4 culture dish, in exsiccator, vacuumize to remove and desolvate, at last 40 ℃ of vacuum-dryings to constant weight.
With the above-mentioned PPDO that obtains, make solvent with sym.-tetrachloroethane, record limiting viscosity [η] with Ubbelohde viscometer in 25 ℃ and be respectively 0.31,0.070,0.060,0.046.
Embodiment 17
Elder generation is 1.68 98 parts of granular PPDO, ZnCl with initial intrinsic viscosity [η]
22 parts of pre-mixing 5min in high-speed mixer; then the mixture after the pre-mixing is added in the twin screw extruder; 80～120 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained PPDO with sym.-tetrachloroethane and phenol (3/2, W/W) make solvent, record limiting viscosity [η] with Ubbelohde viscometer in 25 ℃ and drop to 0.98.
Embodiment 18
Elder generation is 1.68 98 parts of granular PPDO, AlCl with initial intrinsic viscosity [η]
32 parts of pre-mixing 7min in high-speed mixer; then the mixture after the pre-mixing is added in the twin screw extruder; 80～120 ℃ of temperature, screw speed is a melt blending under the 50rpm, extrudes the back granulation or directly carries out blowing, plastic uptake, injection moulding, spinning, calendering acquisition corresponding articles.The gained PPDO records limiting viscosity [η] with the test condition of embodiment 17 and drops to 0.85.
Claims (9)
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410021996 CN1233686C (en) | 2004-03-11 | 2004-03-11 | Process for preparing fatty polyester with variable degradative speed rate and preparation proces sof product thereof |
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| CN 200410021996 CN1233686C (en) | 2004-03-11 | 2004-03-11 | Process for preparing fatty polyester with variable degradative speed rate and preparation proces sof product thereof |
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| JP5334360B2 (en) * | 2006-06-28 | 2013-11-06 | グンゼ株式会社 | Production of biodegradable absorbable polymer with low metal catalyst content |
| CN108359087B (en) * | 2018-02-12 | 2021-04-13 | 贵州大学 | Low melting point branched polylactic acid and preparation method thereof |
| CN109608690A (en) * | 2018-12-12 | 2019-04-12 | 贵州大学 | The method of fast degradation polylactic acid |
| CN112604622B (en) * | 2020-12-08 | 2022-02-18 | 中国科学院山西煤炭化学研究所 | A kind of method of microwave degrading unsaturated polyester resin |
| WO2022171029A1 (en) * | 2021-02-10 | 2022-08-18 | 上海科技大学 | Polyester degradation method |
| CN113698637B (en) * | 2021-08-11 | 2023-08-22 | 兰州鑫银环橡塑制品有限公司 | A kind of fully biodegradable film material for tobacco planting and preparation method thereof |
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