CN1298764C - Method for preparing poly-lactic acid with high molecular weight by polycondensing lactic acid directly - Google Patents
Method for preparing poly-lactic acid with high molecular weight by polycondensing lactic acid directly Download PDFInfo
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- CN1298764C CN1298764C CNB031153216A CN03115321A CN1298764C CN 1298764 C CN1298764 C CN 1298764C CN B031153216 A CNB031153216 A CN B031153216A CN 03115321 A CN03115321 A CN 03115321A CN 1298764 C CN1298764 C CN 1298764C
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- lactic acid
- acid
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 19
- 239000004310 lactic acid Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 21
- 229940059574 pentaerithrityl Drugs 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical group [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims 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 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- IPSRAFUHLHIWAR-UHFFFAOYSA-N zinc;ethane Chemical group [Zn+2].[CH2-]C.[CH2-]C IPSRAFUHLHIWAR-UHFFFAOYSA-N 0.000 claims description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 2
- 150000004706 metal oxides Chemical class 0.000 claims 2
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 26
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 150000007519 polyprotic acids Polymers 0.000 abstract 1
- -1 Poly(lactic acid) Polymers 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 9
- 238000012643 polycondensation polymerization Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical group C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SSTNIXFHCIOCJI-UHFFFAOYSA-N 1-methyl-4-phenoxybenzene Chemical compound C1=CC(C)=CC=C1OC1=CC=CC=C1 SSTNIXFHCIOCJI-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a method for preparing high molecular weight polylactic acid by directly polycondensing lactic acid, which uses polyatomic alcohol and polybasic acid as chain extenders and uses a molecular sieve to remove water in original position to shorten the reaction period and increase the molecular weight. Because the polylactic acid prepared by the present invention has simple technology and low cost, the polylactic acid can be applied to the high value medical field. Moreover, as an environmental-friendly general-purpose plastic, the polylactic acid can also be widely applied to various fields.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the method that a kind of lactic acid direct condensation prepares poly-lactic acid in high molecular weight.
Background technology
Along with the development of Science ﹠ Society, environment and resource problem more and more are subject to people's attention, and become global problem.Oil is that the plastic material of raw material is widely used, and this class material uses the back to be difficult to recycle, and has caused present more serious " white pollution " problem; And this class resource of oil is non-renewable, and a large amount of irrational uses has brought serious shortage of resources problem to the mankind.The raw-material recyclability of the appearance of degradable material, especially degradable material is for the effective means that provide are provided.
Poly(lactic acid) (PLA) is that more relatively a kind of degradable material is used in research at present, it is to be a kind of environment-friendly material that basic raw material prepares with the lactic acid that amylofermentation (or chemosynthesis) obtains, it not only has good physicals, also have excellent biological compatibility and degradation property, and nontoxic non-stimulated to human body.But the applicability poly(lactic acid) overwhelming majority obtains by the two-step approach preparation at present, promptly earlier obtains rac-Lactide by lactic acid through oligomerisation and Pintsch process, carries out the catalysis ring-opening polymerization then and prepares poly(lactic acid).Two-step approach prepares that process is loaded down with trivial details, cost is high, and the price of the poly(lactic acid) that obtains exceeds doubly a lot of than common material, only obtained some application at medical field.Poly(lactic acid) also is not used widely as a kind of general-purpose plastics material.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of technology, the method for preparing poly-lactic acid in high molecular weight with low cost.
The method for preparing poly-lactic acid in high molecular weight that the present invention proposes is a kind of lactic acid direct polycondensation method, the steps include:
1. to the material acid processed
Processed can adopt the decompression dewatering process.Promptly under appropriate vacuum degree and temperature condition, reduce pressure and remove moisture content.Temperature for removing water is 70 ℃ ~ 150., more excellent temperature for removing water is 90 ℃ ~ 110. Vacuum tightness is 10 ~ 200mmHg, and more excellent vacuum tightness is 70 ~ 100mmHg.In the presence of inert gas flow, dewater, both can accelerate dehydration, can reduce side reaction again.Employed rare gas element can be N
2, He etc. (down with).In the decompression dehydration process, use agitator to stir also and can improve dewatering efficiency.
2. precondensation
With the lactic acid that obtains through processed is raw material, under the condition that catalyzer, chainextender and azeotropic organic solvent exist, carries out precondensation.
Employed catalyzer mainly is divided three classes, (1) metal of II, III, IV and V family in the periodic table of elements, as magnesium, aluminium, titanium, zinc, tin etc.: the oxide compound of (2) II, III, IV and V family metal, as magnesium oxide, titanium dioxide, zinc oxide, zirconium dioxide, aluminum oxide etc.; (3) salt of the metal of II, III, IV and V family is as tin protochloride, stannous octoate, zinc ethyl, etheric acid aluminium, tin acetate, manganese acetate, Cobaltous diacetate etc.
Employed azeotropic organic solvent mainly is divided into five classes, and (1) hydrocarbon (hydrocarbon) is as toluene, dimethylbenzene etc.; (2) halogenated hydrocarbon is as chlorobenzene, bromobenzene etc.; (3) ketone is as benzophenone, methyl phenyl ketone etc.; (4) ethers is as dibutyl ether, methyl-phenoxide etc.; (5) alkylation diphenyl ether is as 4-methyl diphenyl ether etc.
Employed chainextender can be polyvalent alcohol, as tetramethylolmethane, sorbyl alcohol, polyvinyl alcohol etc.; Employed chainextender also can be polyprotonic acid, as the stupid tetracarboxylic acid of neighbour, 1,4,5, and 8-naphthalenetetracarbacidic acidic, ethylenediamine tetraacetic acid (EDTA), 3,3,4,4-benzophenone tetracid etc.
Owing to use azeotropic solvent, need the lower end of condenser in reaction unit to insert water trap, make the solvent and the water sepn of condensation, and be back in the reactor and recycle; And in order to remove a spot of water in the reflux solvent, need in reaction unit, to insert the moisture eliminator that contains molecular sieve, guarantee that the solvent that is back in the reactor is not moisture, thereby make polymerization process to carry out smoothly.
In the precondensation process, temperature of reaction is 80 ℃-160 ℃, and more excellent temperature of reaction is 100 ℃-140 ℃; Vacuum tightness is 10-200mmHg, and more excellent vacuum tightness is 50-100mmHg; Reaction times is 3-10 hour.Should adopt in the reaction process from low temperature, the operational path that heats up to high temperature of temperature.Progressively heat up and carry out polymerization and can prevent the more lactic raw material of loss in the reaction process; Feed rare gas element in the reaction process, under the Circulation of inert gas flow, can accelerate reaction process, and can reduce the generation of side reaction.By the reaction of this step, can obtain the lactic acid polymer that molecular weight is 1000-10000.
3. condensation polymerization
Add molecular sieve (generally can be the molecular sieve of 3 -5 ) in the product of precondensation, condensation temperature is 100 ℃-200 ℃, and more excellent condensation temperature is 130 ℃-180 ℃; Vacuum tightness is 0.1-100mmHg, and more excellent vacuum tightness is below the 30mmHg.Under protection of inert gas, continue azeotropic dehydration reaction 8-15 hour, can obtain the poly(lactic acid) that molecular weight is 30000-200000.
The process of the direct combined reaction of lactic acid as shown in the formula:
The inventive method technology is simple, and production cost reduces greatly, and prepared polylactic acid molecule amount height, not only can be applicable to medical field, and can be applicable to wide spectrums such as industry, agricultural, science and technology as a kind of eco-friendly general-purpose plastics.
Embodiment
Specifically describe the present invention below by embodiment.
Embodiment 1:
Is furnished with thermometer to 500ml, agitator, adding 150 gram purity are 85% L-lactic acid and 0.1 tetramethylolmethane that restrains in the four-necked bottle of nitrogen ingress pipe and moisture eliminator, feed nitrogen, be heated to 100 ℃, vacuum tightness is to stir dehydration 2 hours under the condition of 80mmHg, after approximately removing the water of 40 grams, add the antimonous oxide of 0.1 gram and the phenyl ether of 150ml, in reaction unit, insert water trap and the moisture eliminator that molecular sieve is housed, add a certain amount of phenyl ether in the water trap, progressively be warmed up to 140 ℃ from 100 ℃, vacuum tightness is precondensation 5 hours under the 50mmHg, obtain weight-average molecular weight and be 5600 lactic acid polymer, in four-necked bottle, add the molecular sieve of 40 grams, 3 , be warming up to 160 ℃, vacuum tightness is condensation polymerization 10 hours under the 5mmHg condition, obtains weight-average molecular weight and be 56000 poly(lactic acid).
Embodiment 2:
Is furnished with thermometer to 500ml, agitator, adding 150 gram purity are 85% L-lactic acid and 0.25 tetramethylolmethane that restrains in the four-necked bottle of nitrogen ingress pipe and moisture eliminator, feed nitrogen, be heated to 100 ℃, vacuum tightness is to stir dehydration 2 hours under the condition of 80mmHg, after approximately removing the water of 40 grams, add the antimonous oxide of 0.1 gram and the phenyl ether of 150ml, in reaction unit, insert water trap and the moisture eliminator that molecular sieve is housed, add a certain amount of phenyl ether in the water trap, progressively be warmed up to 140 ℃ from 100 ℃, vacuum tightness is precondensation 5 hours under the 50mmHg, obtain weight-average molecular weight and be 6700 lactic acid polymer, in four-necked bottle, add the molecular sieve of 40 grams, 4 , be warming up to 160 ℃, vacuum tightness is condensation polymerization 10 hours under the 5mmHg condition, obtains 97 grammes per square metre average molecular weights and be 89000 poly(lactic acid).
Embodiment 3:
Is furnished with thermometer to 500ml, agitator, adding 150 gram purity are 85% L-lactic acid and 0.5 tetramethylolmethane that restrains in the four-necked bottle of nitrogen ingress pipe and moisture eliminator, feed nitrogen, be heated to 100 ℃, vacuum tightness is to stir dehydration 2 hours under the condition of 80mmHg, after approximately removing the water of 40 grams, add the antimonous oxide of 0.1 gram and the phenyl ether of 150ml, in reaction unit, insert water trap and the moisture eliminator that molecular sieve is housed, add a certain amount of phenyl ether in the water trap, progressively be warmed up to 140 ℃ from 100 ℃, vacuum tightness is precondensation 5 hours under the 50mmHg, obtain weight-average molecular weight and be 4700 lactic acid polymer, in four-necked bottle, add the molecular sieve of 40 grams, 4 , be warming up to 160 ℃, vacuum tightness is condensation polymerization 10 hours under the 5mmHg condition, obtains 93 grammes per square metre average molecular weights and be 64000 poly(lactic acid).
Embodiment 4:
Is furnished with thermometer to 500ml, agitator, adding 150 gram purity are 85% L-lactic acid and 0.1 tetramethylolmethane that restrains in the four-necked bottle of nitrogen ingress pipe and moisture eliminator, feed nitrogen, be heated to 100 ℃, vacuum tightness is to stir dehydration 2 hours under the condition of 80mmHg, after approximately removing the water of 40 grams, add the glass putty of 0.5 gram and the phenyl ether of 150ml, in reaction unit, insert water trap and the moisture eliminator that molecular sieve is housed, add a certain amount of phenyl ether in the water trap, progressively be warmed up to 140 ℃ from 100 ℃, vacuum tightness is precondensation 5 hours under the 50mmHg, obtain weight-average molecular weight and be 7500 lactic acid polymer, in four-necked bottle, add the molecular sieve of 40 grams, 5 , be warming up to 150 ℃, vacuum tightness is condensation polymerization 10 hours under the 5mmHg condition, obtains 100 grammes per square metre average molecular weights and be 71000 poly(lactic acid).
Embodiment 5:
Is furnished with thermometer to 500ml, agitator, adding 150 gram purity are 85% L-lactic acid and 0.1 tetramethylolmethane that restrains in the four-necked bottle of nitrogen ingress pipe and moisture eliminator, feed nitrogen, be heated to 100 ℃, vacuum tightness is to stir dehydration 2 hours under the condition of 80mmHg, after approximately removing the water of 40 grams, add the tin protochloride of 0.2 gram and the phenyl ether of 150ml, in reaction unit, insert water trap and the moisture eliminator that molecular sieve is housed, add a certain amount of phenyl ether in the water trap, progressively be warmed up to 140 ℃ from 100 ℃, vacuum tightness is precondensation 5 hours under the 50mmHg, obtain weight-average molecular weight and be 5000 lactic acid polymer, in four-necked bottle, add the molecular sieve of 40 grams, 5 , be warming up to 160 ℃, vacuum tightness is condensation polymerization 10 hours under the 5mmHg condition, obtains 94 grammes per square metre average molecular weights and be 74000 poly(lactic acid).
Embodiment 6:
Tetramethylolmethane among the embodiment 2 is replaced with sorbyl alcohol, and all the other conditions are the same, obtain 93 grammes per square metre average molecular weights at last and be 63000 poly(lactic acid).
Embodiment 7:
Tetramethylolmethane among the embodiment 2 is replaced with polyvinyl alcohol, and all the other conditions are the same, obtain 91 grammes per square metre average molecular weights at last and be 58000 poly(lactic acid).
Embodiment 8:
Tetramethylolmethane among the embodiment 2 is replaced with adjacent stupid tetracarboxylic acid, and all the other conditions are the same, obtain 92.5 grammes per square metre average molecular weights at last and be 58000 poly(lactic acid).
Embodiment 9:
Tetramethylolmethane among the embodiment 2 is replaced with ethylenediamine tetraacetic acid (EDTA), and all the other conditions are the same, obtain 92.5 grammes per square metre average molecular weights at last and be 74000 poly(lactic acid).
Embodiment 10:
Phenyl ether among the embodiment 2 is replaced with dimethylbenzene, and all the other conditions are the same, obtain 95 grammes per square metre average molecular weights at last and be 61000 poly(lactic acid).
Embodiment 11:
Phenyl ether among the embodiment 2 is replaced with perhydronaphthalene, and all the other conditions are the same, obtain 96 grammes per square metre average molecular weights at last and be 82000 poly(lactic acid).
Embodiment 12:
Phenyl ether among the embodiment 2 is replaced with benzophenone, and all the other conditions are the same, obtain 91.6 grammes per square metre average molecular weights at last and be 56000 poly(lactic acid).
Relatively implement 1:
Is furnished with thermometer to 500ml, agitator, adding 150 gram purity are 85% L-lactic acid in the four-necked bottle of nitrogen ingress pipe and moisture eliminator, feed nitrogen, be heated to 100 ℃, vacuum tightness is to stir dehydration 2 hours under the condition of 80mmHg, after approximately removing the water of 40 grams, add the antimonous oxide of 0.1 gram and the phenyl ether of 150ml, in reaction unit, insert water trap and the moisture eliminator that molecular sieve is housed, add a certain amount of phenyl ether in the water trap, progressively be warmed up to 140 ℃ from 100 ℃, vacuum tightness is precondensation 5 hours under the 50mmHg, obtain weight-average molecular weight and be 4300 lactic acid polymer, be warming up to 160 ℃, vacuum tightness is condensation polymerization 10 hours under the 5mmHg condition, obtains 89 grammes per square metre average molecular weights and be 17000 poly(lactic acid).
Relatively implement 2:
Is furnished with thermometer to 500ml, agitator, adding 150 gram purity are 85% L-lactic acid and 0.25 tetramethylolmethane that restrains in the four-necked bottle of nitrogen ingress pipe and moisture eliminator, feed nitrogen, be heated to 100 ℃, vacuum tightness is to stir dehydration 2 hours under the condition of 80mmHg, after approximately removing the water of 40 grams, add the antimonous oxide of 0.1 gram and the phenyl ether of 150ml, in reaction unit, insert water trap and the moisture eliminator that molecular sieve is housed, add a certain amount of phenyl ether in the water trap, progressively be warmed up to 140 ℃ from 100 ℃, vacuum tightness is precondensation 5 hours under the 50mmHg, obtain weight-average molecular weight and be 6700 lactic acid polymer, be warming up to 160 ℃, vacuum tightness is condensation polymerization 10 hours under the 5mmHg condition, obtains 95 grammes per square metre average molecular weights and be 57000 poly(lactic acid).
Claims (5)
1, a kind of lactic acid direct condensation prepares the method for poly-lactic acid in high molecular weight, it is characterized in that concrete steps are as follows:
(1) to the material acid processed: adopt the decompression dewatering process, temperature for removing water is 75-150 ℃, and vacuum tightness is 10-200mmHg, carries out in the presence of rare gas element;
(2) precondensation is a raw material with the lactic acid through processed, under catalyzer, chainextender and azeotropic organic solvent existence condition, carries out precondensation; Employed catalyzer is the metal of II, III, IV and V family in the periodic table of elements, or its metal oxide, or its metal-salt; Employed azeotropic organic solvent is the one of the following kind: hydrocarbon, halogenated hydrocarbon, ketone, ethers, alkylation diphenyl ether; Employed chainextender is polyvalent alcohol or polyprotonic acid; Reaction conditions is: temperature 80-160 ℃, and vacuum tightness 10-200mmHg, time 3-10 hour;
(3) polycondensation adds molecular sieve in the product of precondensation, condensation temperature is 100-200 ℃, and vacuum tightness is 0.1-100mmHg, and the azeotropic dehydration reaction is 8-15 hour under protection of inert gas.
2, preparation method according to claim 1, in the catalyzer that it is characterized in that using in the precondensation process, metal is magnesium, aluminium, zinc, titanium or tin; Metal oxide is magnesium oxide, titanium dioxide, zinc oxide, zirconium dioxide or aluminum oxide; Metal-salt is tin protochloride, stannous octoate, zinc ethyl, etheric acid aluminium, tin acetate, manganese acetate or Cobaltous diacetate.
3, preparation method according to claim 1 is characterized in that employed polyvalent alcohol chainextender is tetramethylolmethane, sorbyl alcohol or polyvinyl alcohol; Employed polyprotonic acid chainextender is an adjacent benzene tetracarboxylic acid, 1,4,5,8-naphthalenetetracarbacidic acidic, ethylenediamine tetraacetic acid (EDTA) or 3,3,4,4-benzophenone tetracid.
4, preparation method according to claim 1 is characterized in that the prepolymerization reaction process is connected with rare gas element.
5, preparation method according to claim 1 is characterized in that in the prepolymerization reaction, inserts water trap in the condenser lower end of reaction unit, makes the solvent and the water sepn of condensation, and is back in the reactor and recycles; In reaction unit, insert the moisture eliminator that contains molecular sieve, guarantee that the solvent that is back in the reactor is not moisture.
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| CN100424111C (en) * | 2004-03-25 | 2008-10-08 | 上海同杰良生物材料有限公司 | Method for preparing highly branched polylactic acid by bulk polymerization |
| CN1325533C (en) * | 2004-03-25 | 2007-07-11 | 上海同杰良生物材料有限公司 | Direct fusion method for preparing poly lactic acid in high molecular weight |
| CN1331912C (en) * | 2004-07-07 | 2007-08-15 | 同济大学 | Method of preparing high molecular weight polylactic acid using solid phase polymerization |
| CN1295264C (en) * | 2004-07-15 | 2007-01-17 | 合肥工业大学 | Method for preparing high molecular weight poly-L-lactic acid by melt polycondensation-solid phase polymerization |
| CN101747501B (en) * | 2008-12-12 | 2011-10-26 | 北京服装学院 | Method for synthesizing high molecular weight polylactic acid |
| CN103300120B (en) * | 2013-06-25 | 2015-04-22 | 南京工业大学 | Green poultry and livestock depilating agent and preparation method thereof |
| CN108610473A (en) * | 2018-05-09 | 2018-10-02 | 上海昶法新材料有限公司 | A kind of method of synthesizing polylactic acid |
| CN114213638A (en) * | 2021-11-16 | 2022-03-22 | 元嘉生物科技(浙江)有限公司 | Method for improving polylactic acid molecular weight based on in-situ drying dehydration |
| CN114621179B (en) * | 2022-03-17 | 2024-03-26 | 中国神华煤制油化工有限公司 | Synthesis method of glycolide |
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| US5401796A (en) * | 1993-04-02 | 1995-03-28 | Mitsui Toatsu Chemicals, Inc. | Aliphatic polyester and preparation process thereof |
| JP2001040079A (en) * | 1999-08-02 | 2001-02-13 | Nishikawa Rubber Co Ltd | Biodegradable resin and its production |
| CN1298892A (en) * | 1999-12-09 | 2001-06-13 | 浙江大学 | Process for preparing biodegradable polylactate material by direct polycondensation of lactic acid |
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| US5401796A (en) * | 1993-04-02 | 1995-03-28 | Mitsui Toatsu Chemicals, Inc. | Aliphatic polyester and preparation process thereof |
| JP2001040079A (en) * | 1999-08-02 | 2001-02-13 | Nishikawa Rubber Co Ltd | Biodegradable resin and its production |
| CN1298892A (en) * | 1999-12-09 | 2001-06-13 | 浙江大学 | Process for preparing biodegradable polylactate material by direct polycondensation of lactic acid |
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