CN1718607A - Solid state polymerization prepares the method for poly-lactic acid in high molecular weight - Google Patents
Solid state polymerization prepares the method for poly-lactic acid in high molecular weight Download PDFInfo
- Publication number
- CN1718607A CN1718607A CN 200410052604 CN200410052604A CN1718607A CN 1718607 A CN1718607 A CN 1718607A CN 200410052604 CN200410052604 CN 200410052604 CN 200410052604 A CN200410052604 A CN 200410052604A CN 1718607 A CN1718607 A CN 1718607A
- Authority
- CN
- China
- Prior art keywords
- lactic acid
- poly
- molecular weight
- solid state
- state polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000007787 solid Substances 0.000 title claims abstract description 30
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 22
- -1 poly(lactic acid) Polymers 0.000 claims abstract description 63
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 43
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 13
- 238000010298 pulverizing process Methods 0.000 claims description 13
- 235000011150 stannous chloride Nutrition 0.000 claims description 13
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 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
- 239000003054 catalyst Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 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 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [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
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium 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
- 230000000737 periodic effect Effects 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 230000004927 fusion Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 241000237502 Ostreidae Species 0.000 description 9
- 235000020636 oyster Nutrition 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000008187 granular material Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical class CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of solid state polymerization prepares the method for poly-lactic acid in high molecular weight.This method utilizes direct polycondensation method to prepare the poly(lactic acid) prepolymer, utilizes solid state polymerization to the further polymerization of prepolymer then.The present invention prepares prepolymer by the cheap relatively fusion direct polycondensation method of cost; utilize power consumption solid state polymerization still less further to improve molecular weight then; therefore; the poly-lactic acid in high molecular weight that the cost for preparing with this method is quite cheap not only can be used for the medical field of high value; can also obtain using more widely as a kind of eco-friendly general-purpose plastics, be expected to alleviate the agricultural-food problem of outlet of oil crisis, white pollution and China simultaneously.
Description
Technical field
The present invention relates to the preparation method of poly(lactic acid), particularly a kind of solid state polymerization prepares the method for poly-lactic acid in high molecular weight.
Background technology
Along with the progress of science and the development of society, shortage of resources and environmental pollution problems become increasingly conspicuous, and have become the global problem of people's extensive concern.According to scholarly forecast, the oil in the whole world will be exploited totally in 50 years, therefore, be that the plastic material of raw material will face a crisis when the time comes with the oil; In addition, present widely used plastic material goods are difficult to recycling after use, caused serious day by day " white pollution ".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) a kind of degradable material that utilize to be worth that has very much that comes to this, it is to be a kind of environment-friendly material that basic raw material prepares with the lactic acid that renewable resources (as: corn) obtains.If can significantly reduce its production cost, make it will effectively solve the agricultural-food problem of outlet of oil crisis, white pollution and China as the general-purpose plastics widespread use.
High molecular weight polylactic acid mainly is by ring-opening polymerization at present, among the patent JP56-14688, obtains the lactide dimer of lactic acid earlier, prepares high molecular weight polylactic acid through ring-opening polymerization again, and shortcoming is that cost is too high, has seriously limited practical application.
The another kind of method of preparation poly(lactic acid) is a direct polycondensation method, and among the patent JP59-96123, under the condition that catalyzer exists, direct condensation prepares poly(lactic acid) under the decompression hot conditions, yet the polylactic acid molecule amount that obtains is very low, is difficult to be extensive use of as a kind of material; Among the patent US4273920, use strong-acid ion exchange resin, direct condensation prepares gained polylactic acid molecule amount can reach 30,000.The advantage of direct polycondensation method is that production cost is low, but its molecular weight that can reach still can't satisfy the requirement that poly(lactic acid) is used as general-purpose plastics.
Method for solid phase polymerization is to be lower than the fusing point of prepolymer and to be higher than a kind of polymerization process that its second-order transition temperature carries out at polymerization temperature.Be characterized in that polymerization temperature is low, can obviously reduce generation, and can promote the raising of the relative molecular weight of the raising of residual monomer transformation efficiency and polymkeric substance because of the polymer degradation side reaction that causes of heat.Solid state polymerization has had successful application as a kind of traditional polymerization process in the production of materials such as terylene, nylon, polycarbonate.Patent US96-00330 utilizes the solid state polymerization of lower molecular weight polyethylene terephthalate to produce the higher molecular weight dacron product of unique physical form.Among the patent CN1348973A, will carry out solid state polymerization, and make and have tensility and full-bodied Nylon 6 based on the mixture of common Nylon 6.Poly(lactic acid) belongs to the intramolecularly polycondensation as a kind of new polyester material on polymerization methods, though same terylene, nylon etc. have certain difference on production technique, in theory still exist and utilize solid state polymerization to improve the possibility of its molecular weight.
Summary of the invention
The object of the present invention is to provide a kind of solid state polymerization to prepare the method for poly-lactic acid in high molecular weight.
For reaching above-mentioned purpose, the present invention is achieved in that
A kind of solid state polymerization prepares the method for poly-lactic acid in high molecular weight, at first carries out the body precondensation, is raw material with the lactic acid that obtains behind dewatering process, under the condition that catalyzer exists, carries out the body precondensation.In polycondensation process, temperature of reaction is 80 ℃～200 ℃, and more excellent temperature of reaction is 100 ℃～180 ℃; Vacuum tightness is 0～50mmHg, and more excellent vacuum tightness is 0～10mmHg; Reaction times is 5～50 hours.Adopt the operational path of low temperature high vacuum, middle temperature high vacuum and high temperature high vacuum in the reaction process, 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 at times, under the Circulation of inert gas flow, can accelerate reaction process, and can reduce the generation of side reaction.Through polycondensation, can obtain weight-average molecular weight and be 1,000～100,000 poly(lactic acid) prepolymer.
Next carries out the pre-crystallization treatment and the pulverizing of prepolymer, and the prepolymer that mass polymerization prepares is put into crystallizer, carries out crystallization under isothermal condition, and 60～180 ℃ of Tcs, more excellent Tc are 80～160 ℃.Crystallization time is 0.5～10 hour, and more excellent crystallization time is 1～5 hour.Keep vacuum state in the crystallizer or feed protection of inert gas.To be ground into fine particle through the crystalline poly(lactic acid), particle diameter is at 0～200 order, and more excellent particle diameter is 20～160 orders.
Carry out solid state polymerization at last, carry out solid state polymerization putting into rotatable reactor through pulverizing poly(lactic acid) fine particle after the crystallization.60～200 ℃ of system temperatures, more excellent temperature are 100～180 ℃; Constantly taking out negative pressure keeps high vacuum or feeds circulated inert gas stream (as N
2, He etc.) condition under reacted 1～100 hour, the more excellent reaction times is 10～80 hours; Vacuum tightness is 0～50mmHg, and more excellent vacuum tightness is below the 20mmHg.Catalyst levels is generally the 0.01wt%～5wt% of prepolymer, and that more excellent is 0.1wt%～2wt%.
Employed catalyzer mainly is divided into four classes, and the metal of II, III, IV and V family in (1) periodictable is as magnesium, aluminium, titanium, zinc, tin etc.; (2) oxide compound of II, III, IV and V family metal is as magnesium oxide, titanium dioxide, zinc oxide, titanium dioxide pick, 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.; (4) use the binary catalyst system as promotor and metal, metal oxide or metal-salt composition such as organic sulfonic acid, metal alkylide.
In order to improve solid-phase polymerization speed, can under higher temperature of reaction, carry out polycondensation.If yet under higher temperature, reacting at the very start, prepolyer granule is adhered to one another easily, makes the difficulty more that removes of micromolecular water, has accelerated depolymerization reaction, is difficult to obtain high molecular weight polylactic acid.Therefore, the present invention adopts the polymerization route that progressively heats up, and promptly carries out under relatively lower temp earlier, along with the molecular weight of poly(lactic acid) and the progressively raising of degree of crystallinity, progressively improves temperature of reaction then.This method can be avoided the adhered to one another of poly(lactic acid) particle on the one hand; Improved the ceiling temperature of solid state polymerization on the other hand, thereby accelerated speed of response, can make high molecular weight polylactic acid in the short reaction times.Progressively the speed of Sheng Wening is 1～50 ℃/5 hours.More excellent is 5～30 ℃/5 hours.
In solid state polymerization processes, can make reactor be 45 degree rotations in order to improve polymerization rate.In low speed rotation polymer beads is rolled in reactor together with dewatering agent, high speed rotating can produce centrifugation, all in various degree help accelerating deviating from of water.
Also can be used the use of dewatering agent in solid state polymerization processes, the usage quantity of dewatering agent is generally 1.1～2.0 times of theoretical consumption.Selecting for use of dewatering agent is generally the stable chemical classes dewatering agent of proterties that strong dehydrating effect is arranged in the solid phase polymerization temperature scope, as Na, K, metal oxide, acid, alkali, the inorganic salt and composition thereof that can form crystal water or physics class dewatering agent, as various pore sorbent materials and various dehydration property resin.Preferred chemical classes dewatering agent is CaO, anhydrous CaCl, anhydrous CaSO
4, anhydrous CuSO
4Or P
2O
5Preferred physics class dewatering agent is silica gel, molecular sieve, acrylic resin or montmorillonite.Repeateds use of can regenerating eaily after physics class dewatering agent uses, so help saving cost.
The invention has the beneficial effects as follows: adopt low cost, the purified mass polymerization of product to prepare the poly(lactic acid) prepolymer, utilize solid state polymerization further to improve its molecular weight then, perplex the expensive and low-molecular-weight problem that poly(lactic acid) is used as general-purpose plastics always thereby solved.Utilize solid state polymerization, weight-average molecular weight can surpass 300,000, and product is pure and reduced production cost significantly.
Embodiment
Specify the present invention and beneficial effect thereof below in conjunction with embodiment.
Embodiment 1:
In 2 liters of four-necked bottles of being furnished with thermometer, agitator and nitrogen ingress pipe, add 250 gram purity and be 85% L-lactic acid, feed nitrogen, be heated to 100 ℃, vacuum tightness is to stir dehydration 2 hours under the condition of 80mmHg, approximately remove the water of 30 grams after, add 0.2 gram catalyzer tin protochloride, progressively be warmed up to 160 ℃ from 100 ℃, vacuum tightness is polycondensation 10 hours under the 40mmHg, obtains weight-average molecular weight and be 21,507 poly(lactic acid) prepolymer.
Embodiment 2:
In 2 liters of four-necked bottles of being furnished with thermometer, agitator and nitrogen ingress pipe, add 250 gram purity and be 85% L-lactic acid, feed nitrogen, be heated to 100 ℃, vacuum tightness is to stir dehydration 2 hours under the condition of 80mmHg, approximately remove the water of 30 grams after, add 0.1 gram catalyzer tin protochloride, progressively be warmed up to 170 ℃ from 100 ℃, vacuum tightness is polycondensation 20 hours under the 20mmHg, obtains weight-average molecular weight and be 57,423 poly(lactic acid) prepolymer.
Embodiment 3:
Getting 5 grams is the prepolymer of basis preparation with embodiment 1,80 ℃ of following isothermal crystals take out pulverizing after 2 hours in crystallizer, mixed 0.05 gram catalyzer tin protochloride adds in the rotatable reactor, be heated to 140 ℃, continue to react 30 hours under the condition of vacuumizing, vacuum tightness is less than 40mmHg, and the reactor speed of rotation is 50 commentaries on classics/min, obtain weight-average molecular weight at last and be 70,162 oyster white poly(lactic acid).
Embodiment 4:
Getting 5 grams is the prepolymer of basis preparation with embodiment 1,80 ℃ of following isothermal crystals take out pulverizing after 2 hours in crystallizer, mixed 0.05 gram catalyzer tin protochloride adds in the rotatable reactor, be heated to 150 ℃, continue to react 25 hours under the condition of vacuumizing, vacuum tightness is less than 40mmHg, and the reactor speed of rotation is 70 commentaries on classics/min, obtain weight-average molecular weight at last and be 115,455 oyster white poly(lactic acid).
Embodiment 5:
Getting 5 grams is the prepolymer of basis preparation with embodiment 1,80 ℃ of following isothermal crystals take out pulverizing after 2 hours in crystallizer, mixed 0.1 gram catalyzer tin protochloride adds in the rotatable reactor, be heated to 155 ℃, continue to react 20 hours under the condition of vacuumizing, vacuum tightness is less than 40mmHg, and the reactor speed of rotation is 100 commentaries on classics/min, obtain weight-average molecular weight at last and be 152,946 oyster white poly(lactic acid).
Embodiment 6:
Getting 5 grams is the prepolymer of basis preparation with embodiment 2,90 ℃ of following isothermal crystals take out pulverizing after 5 hours in crystallizer, mixed 0.1 gram catalyzer tin protochloride adds in the rotatable reactor, be heated to 160 ℃, continue to react 15 hours under the condition of vacuumizing, vacuum tightness is less than 20mmHg, and the reactor speed of rotation is 100 commentaries on classics/min, obtain weight-average molecular weight at last and be 246,779 oyster white poly(lactic acid).
Embodiment 7～13:
Based on embodiment 3, change catalyzer, the result is as follows:
The weight-average molecular weight of catalyzer poly(lactic acid)
Glass putty 51,877
Zinc powder 47,969
Stannous octoate 60,120
Dibutyl tin dilaurate 54,199
Aluminum oxide 45,851
Antimonous oxide 38,294
Tin protochloride/tosic acid (mol ratio 2: 1) 79,431
Embodiment 14～16:
Based on embodiment 4, change the weight percent of catalyzer and prepolymer, the result is as follows:
The weight-average molecular weight of catalyzer/prepolymer (wt%) poly(lactic acid)
0.4 119,283
1.2 107,428
2 86,922
Embodiment 17～23:
Based on embodiment 5, change dewatering agent, the result is as follows:
The weight-average molecular weight of dewatering agent poly(lactic acid)
Calcium Chloride Powder Anhydrous 82,904
Calcium oxide 88,673
Anhydrous calciumsulphate 74,557
Anhydrous cupric sulfate 71,301
Molecular sieve 5A 93,637
Molecular sieve 4A 95,135
Silica gel 73,426
Embodiment 24:
Getting 5 grams is the prepolymer of basis preparation with embodiment 1,80 ℃ of following isothermal crystals take out pulverizing after 2 hours in crystallizer, filtering out particle diameter is 40～60 purpose prepolyer granules, mixed 0.05 gram catalyzer glass putty adds in the rotatable reactor, is heated to 160 ℃, continues to react 35 hours under the condition of vacuumizing, vacuum tightness is less than 20mmHg, the reactor speed of rotation is 70 commentaries on classics/min, obtains weight-average molecular weight at last and be 196,105 oyster white poly(lactic acid).
Embodiment 25～28:
Based on embodiment 24, change the prepolymer particle diameter, the result is as follows:
The weight-average molecular weight of particle diameter (order) poly(lactic acid)
20～40 188,861
60～80 198,089
80～100 179,173
120～140 168,160
160～180 158,990
Embodiment 29～31:
Based on embodiment 24, change the reactor speed of rotation, the result is as follows:
Rotating speed (rev/min) weight-average molecular weight of poly(lactic acid)
40 184,611
110 190,743
180 197,429
Embodiment 32:
Getting 5 grams is the prepolymer of basis preparation with embodiment 1,80 ℃ of following isothermal crystals take out pulverizing after 2 hours in crystallizer, filtering out particle diameter is 40～60 purpose prepolyer granules, mixed 0.05 gram catalyzer tin protochloride adds in the rotatable reactor, continue to vacuumize, vacuum tightness progressively is warming up to 160 ℃ less than 20mmHg since 120 ℃, heat-up rate is 10 ℃/5 hours, keeps 5 hours at 160 ℃ at last.The reactor speed of rotation is 70 commentaries on classics/min, obtains weight-average molecular weight at last and be 226,514 oyster white poly(lactic acid).
Embodiment 33:
Getting 5 grams is the prepolymer of basis preparation with embodiment 1,80 ℃ of following isothermal crystals take out pulverizing after 2 hours in crystallizer, filtering out particle diameter is 60～80 purpose prepolyer granules, mixed 0.05 gram catalyzer tin protochloride adds in the rotatable reactor, continue to vacuumize, vacuum tightness progressively is warming up to 170 ℃ less than 20mmHg since 130 ℃, heat-up rate is 10 ℃/5 hours, keeps 5 hours at 170 ℃ at last.The reactor speed of rotation is 40 commentaries on classics/min, obtains weight-average molecular weight at last and be 250,306 oyster white poly(lactic acid).
Embodiment 34:
Getting 5 grams is the prepolymer of basis preparation with embodiment 2,80 ℃ of following isothermal crystals take out pulverizing after 2 hours in crystallizer, filtering out particle diameter is 40～60 purpose prepolyer granules, mixed 0.05 gram catalyzer tin protochloride adds in the rotatable reactor, continue to vacuumize, vacuum tightness progressively is warming up to 170 ℃ less than 40mmHg since 150 ℃, heat-up rate is 5 ℃/5 hours, keeps 10 hours at 170 ℃ at last.The reactor speed of rotation is 80 commentaries on classics/min, obtains weight-average molecular weight at last and be 286,011 oyster white poly(lactic acid).
Embodiment 35:
Getting 5 grams is the prepolymer of basis preparation with embodiment 2,80 ℃ of following isothermal crystals take out pulverizing after 4 hours in crystallizer, filtering out particle diameter is 60～80 purpose prepolyer granules, mixed 0.1 gram catalyzer tin protochloride adds in the rotatable reactor, continue to vacuumize, vacuum tightness progressively is warming up to 170 ℃ less than 40mmHg since 150 ℃, heat-up rate is 5 ℃/5 hours, keeps 8 hours at 170 ℃ at last.The reactor speed of rotation is 40 commentaries on classics/min, obtains weight-average molecular weight at last and be 310,495 oyster white poly(lactic acid).
Simultaneous test 1:
Do not adopt the mode that continues to take out negative pressure, but static vacuum seal reactor, all the other conditions are identical with embodiment 5, and the weight-average molecular weight of the poly(lactic acid) that obtains is 19,472.
Simultaneous test 2:
Reactor is static not to be rotated, and all the other conditions are identical with embodiment 5, and the weight-average molecular weight of the poly(lactic acid) that obtains is 82,168.
Claims (10)
1, a kind of solid state polymerization prepares the method for poly-lactic acid in high molecular weight, may further comprise the steps,
1) body precondensation is a raw material with the lactic acid that obtains behind dewatering process, under the condition that catalyzer exists, carries out the body precondensation, and in polycondensation process, temperature of reaction is 80 ℃～200 ℃; Vacuum tightness is 0～50mmHg, and the reaction times is 5～50 hours, feeds rare gas element in the reaction process at times, through polycondensation, can obtain weight-average molecular weight and be 1,000～100,000 poly(lactic acid) prepolymer,
2) crystallization treatment and pulverizing; the described poly(lactic acid) prepolymer that step 1) obtains is put into crystallizer; 60～180 ℃ of Tcs; crystallization time is 0.5～10 hour; keep vacuum state in the crystallizer or feed protection of inert gas; to be ground into fine particle through the crystalline poly(lactic acid), particle diameter is at 0～200 order
3) solid state polymerization, carry out solid state polymerization to putting into reactor through pulverizing poly(lactic acid) fine particle after the crystallization, 60～200 ℃ of system temperatures, in the reactor for the stationary vacuum state or continue the state of vacuumizing, under the condition that feeds circulated inert gas stream, reacted 1～100 hour, vacuum tightness is 0～50mmHg, and catalyst levels is generally the 0.01wt%～5wt% of prepolymer.
2, solid state polymerization according to claim 1 prepares the method for poly-lactic acid in high molecular weight, it is characterized in that: in described step 1), described temperature of reaction is 100 ℃～180 ℃; Vacuum tightness is 0～10mmHg.
3, solid state polymerization according to claim 1 prepares the method for poly-lactic acid in high molecular weight, it is characterized in that: described step 2), carry out crystallization under isothermal condition, described Tc is 80～100 ℃, crystallization time is 1～5 hour, and the particle diameter that is ground into behind the fine particle is 20～160 orders.
4, solid state polymerization according to claim 1 prepares the method for poly-lactic acid in high molecular weight, it is characterized in that: in the described step 3), system temperature is 100～180 ℃; Reaction times is 10～80 hours; Vacuum tightness is below the 20mmHg, and catalyst levels is 0.1wt%～2wt%.
5, solid state polymerization according to claim 1 prepares the method for poly-lactic acid in high molecular weight, it is characterized in that: described catalyzer is metal, metal oxide or the metal-salt of II, III, IV and V family in the periodic table of elements, perhaps uses organic sulfonic acid, metal alkylide to form catalyzer as promotor and II, III, IV and V family metal, metal oxide or metal-salt.
6, the method for preparing poly-lactic acid in high molecular weight according to the described solid state polymerization of claim 1, it is characterized in that: metal is magnesium, aluminium, titanium, zinc, tin in the described catalyzer, described metal oxide is meant magnesium oxide, titanium dioxide, zinc oxide, titanium dioxide pick, aluminum oxide, and described metal-salt is meant tin protochloride, stannous octoate, zinc ethyl, etheric acid aluminium, tin acetate, manganese acetate, Cobaltous diacetate.
7, solid state polymerization according to claim 1 prepares the method for poly-lactic acid in high molecular weight, it is characterized in that: in the described step 3), described reactor is axially about 45 degree rotations, and rotating speed is 1～200 rev/min, progressively be warming up to described system temperature, heat-up rate is 1～50 ℃/5 hours.
8, solid state polymerization according to claim 7 prepares the method for poly-lactic acid in high molecular weight, it is characterized in that: heat-up rate described in the described step 3) is 5～30 ℃/5 hours.
9, solid state polymerization according to claim 1 prepares the method for poly-lactic acid in high molecular weight, it is characterized in that: in described step 3), be used dewatering agent.
10, aqua is CaO, anhydrous CaCl, anhydrous CaSO
4, anhydrous CuSO
4, P
2O
5, silica gel, molecular sieve, acrylic resin or montmorillonite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100526047A CN1331912C (en) | 2004-07-07 | 2004-07-07 | Method of preparing high molecular weight polylactic acid using solid phase polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100526047A CN1331912C (en) | 2004-07-07 | 2004-07-07 | Method of preparing high molecular weight polylactic acid using solid phase polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1718607A true CN1718607A (en) | 2006-01-11 |
| CN1331912C CN1331912C (en) | 2007-08-15 |
Family
ID=35930562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100526047A Expired - Lifetime CN1331912C (en) | 2004-07-07 | 2004-07-07 | Method of preparing high molecular weight polylactic acid using solid phase polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1331912C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009082924A1 (en) * | 2007-12-24 | 2009-07-09 | Anhui Zhongren Science & Technology Co., Ltd. | A process for preparing high molecular weight poly (l-lactic acid) |
| CN100543060C (en) * | 2006-08-03 | 2009-09-23 | 西安工程大学 | The preparation technology of poly lactic acid in use for spinning |
| CN101497688B (en) * | 2008-01-31 | 2012-06-13 | 东丽纤维研究所（中国）有限公司 | Solid state polymerization method for preparing polylactic acid |
| CN103300120A (en) * | 2013-06-25 | 2013-09-18 | 南京工业大学 | Green poultry and livestock depilating agent and preparation method thereof |
| WO2019057032A1 (en) * | 2017-09-21 | 2019-03-28 | 南京大学 | Process method for recycling by-product polymer residue from the production of glycolide and lactide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1099804A (en) * | 1996-09-30 | 1998-04-21 | Japan Steel Works Ltd:The | Cleaning of batchwise polycondensation reaction tank |
| CN1298764C (en) * | 2003-02-08 | 2007-02-07 | 上海同杰良生物材料有限公司 | Method for preparing poly-lactic acid with high molecular weight by polycondensing lactic acid directly |
-
2004
- 2004-07-07 CN CNB2004100526047A patent/CN1331912C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100543060C (en) * | 2006-08-03 | 2009-09-23 | 西安工程大学 | The preparation technology of poly lactic acid in use for spinning |
| WO2009082924A1 (en) * | 2007-12-24 | 2009-07-09 | Anhui Zhongren Science & Technology Co., Ltd. | A process for preparing high molecular weight poly (l-lactic acid) |
| CN101497688B (en) * | 2008-01-31 | 2012-06-13 | 东丽纤维研究所（中国）有限公司 | Solid state polymerization method for preparing polylactic acid |
| CN103300120A (en) * | 2013-06-25 | 2013-09-18 | 南京工业大学 | Green poultry and livestock depilating agent and preparation method thereof |
| WO2019057032A1 (en) * | 2017-09-21 | 2019-03-28 | 南京大学 | Process method for recycling by-product polymer residue from the production of glycolide and lactide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1331912C (en) | 2007-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1273514C (en) | Process for making polytrimethylene terephthalate | |
| CN101050265A (en) | Wet mild polyurethane resin in use for synthetic leather, and preparation method | |
| CN1066449A (en) | The production method of high molecular weight polyester resins | |
| CN101054435A (en) | Wet-type polyamine resin with hydrolyzation resistance and high peeling strength and preparing method thereof | |
| CN1718607A (en) | Solid state polymerization prepares the method for poly-lactic acid in high molecular weight | |
| CN101649042B (en) | Preparation method of high molecular poly lactic acid | |
| CN1127532C (en) | Process for preparing biodegradable polylactate material by direct polycondensation of lactic acid | |
| CN1785477A (en) | Nano-deoxidant composition and its synthesis method | |
| CN1659208A (en) | Process for producing polyester resin | |
| CN1298764C (en) | Method for preparing poly-lactic acid with high molecular weight by polycondensing lactic acid directly | |
| CN1613889A (en) | Method for preparing high-polymer polylactic on Bitruder | |
| CN1958640A (en) | Technique of preparing poly lactic acid in use for spinning | |
| CN1563139A (en) | Direct fusion method for preparing poly lactic acid in high molecular weight | |
| CN1132868C (en) | Method for preparing high molecular weight poly lactic acid by direct polycondensation | |
| CN1328072A (en) | High-activity catalyst and its application in synthesizing polyester | |
| CN1100614C (en) | Solid catalyst for synthesizing glycol monoether acetate | |
| CN1380140A (en) | Catalyst for synthesizing dimethyl carbonate and its application | |
| CN1796433A (en) | Method for synthesizing polyester by using rare earth catalyst | |
| CN1974662A (en) | Composite elastic chitin whisker material and its prepn and use | |
| TW200302237A (en) | Method for treating polyester polymers and polyester polymers with low content of low-boiling components | |
| TWI229099B (en) | Method of continuous producing for epsilon-caprolactone polymer | |
| CN1289567C (en) | Deduction of friability of poly(trimethylene terephthalate) | |
| CN1563142A (en) | Method for preparing extended chain of poly paradioxygen cyclohexanone/aliphatic polyester and/or coupling biodegradable polymer | |
| CN102850538A (en) | Non-lactic acid hydroxy group-terminated polylactic acid and its preparation method | |
| CN1238400C (en) | Method for chain extending poly paradioxygen cyclohexanone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20070815 |
|
| CX01 | Expiry of patent term |