CN101921468B - Polylactic acid composition containing sulfoacid compound and phosphorus-containing organic compound and preparation method thereof - Google Patents

Polylactic acid composition containing sulfoacid compound and phosphorus-containing organic compound and preparation method thereof Download PDF

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CN101921468B
CN101921468B CN 200910033078 CN200910033078A CN101921468B CN 101921468 B CN101921468 B CN 101921468B CN 200910033078 CN200910033078 CN 200910033078 CN 200910033078 A CN200910033078 A CN 200910033078A CN 101921468 B CN101921468 B CN 101921468B
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sulfoacid
lactic acid
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acid
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CN101921468A (en
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于波
何勇
宋婷婷
左璞晶
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Naphthalene Walker LLC
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Toray Fibers and Textiles Research Laboratories China Co Ltd
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Abstract

The invention discloses a polylactic acid composition containing a sulfoacid compound and a phosphorus-containing organic compound. The polylactic acid composition contains polylactic acid, a nitrogen-containing organic compound and the sulfoacid compound. The invention also discloses a preparation method of the polylactic acid composition containing the sulfoacid compound and a nitrogen-containing organic compound, comprising the following steps of: carrying out melt polycondensation by using bibasic sulfoacid and/or polybasic sulfoacid as a catalyst to obtain a polylactic acid product; and further carrying out solid-phase polymerization to the melt-polycondensation product to obtain high-molecular weight polylactic acid, wherein the nitrogen-containing organic compound can be added to a lactic acid monomer at the beginning of the melt polycondensation or added to the polylactic acid after the melt polycondensation is completed. The polylactic acid composition obtained in the method has higher hydrolysis resistance, higher heat stability and excellent color and luster, and when the polylactic acid composition is processed for 5 days at the condition of the relative humidity of 90% and the temperature of 60 DEG C, the weight-average molecular weight of the polylactic acid is reduced by 50% at most.

Description

A kind of poly (lactic acid) composition that contains sulfoacid compound and organic phosphorus compound and preparation method thereof
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of poly (lactic acid) composition and preparation method thereof.
Background technology
Enter 21 century, environmental pollution and shortage of resources have become global problem, also more and more are subject to people's attention simultaneously.Synthesized polymer material take oil as raw material is widely used, and significant contribution has been made in the development of human civilization.But be difficult to behind this class materials'use recycle, cause at present serious " white pollution " problem; On the other hand, oil is Nonrenewable resources, and more and more a large amount of consumption makes the serious shortage of resources problem of facing mankind.People expect degradative plastics (mainly being aliphatic polyester), the especially research and development of the degradable material of renewable resources origin and use can greatly alleviate this two large problems in the near future.
Poly(lactic acid) (PLA) is a kind of degradable material that relatively many renewable resources origin are used at present research, it be the lactic acid that obtains take amylofermentation (or chemosynthesis) as basic raw material prepare a kind of to the nontoxic non-stimulated environment-friendly material of human body, it not only has good physicals, also has good biocompatibility and degradation property.The factor of restriction poly(lactic acid) widespread use mainly contains following two at present: one is that production cost is high, expensive; Another is to compare with general-purpose plastics, and the resistance toheat of poly(lactic acid) and anti-hydrolytic performance are all relatively poor.
Be shown below, at present poly(lactic acid) preparation method commonly used mainly can be divided into two kinds of ring-opening polymerization method (indirect method) and direct polycondensation methods (direct method):
Figure G2009100330782D00011
(open loop) method is the polymerization route that present most applicability poly(lactic acid) adopts indirectly, but, (open loop) method production technique is tediously long indirectly, complex process, particularly repeatedly purify and recrystallization at lactide refined middle need, consume a large amount of reagent, high production cost has seriously hindered the widespread use of poly(lactic acid) as a kind of general-purpose plastics material.
In recent years, more and more caused people's concern by the method for acid through direct polycondensation by lactic synthesizing polylactic acid.Early report is arranged about the research of Direct Polycondensation of Polylactic Acid is external, recent year also begins to carry out the research of this respect.Its method mainly contains melt phase polycondensation, solution polymerization process, direct condensation+chain extending reaction, solid state polymerization etc., and it respectively has relative merits.
Wherein solid state polymerization is that solid-state oligopolymer is higher than the polyreaction of carrying out under its second-order transition temperature being lower than melting point polymer, and this method can effectively improve the molecular weight of polyester polymer.
The mechanism of solid state polymerization is: at low-molecular-weight poly(lactic acid) performed polymer (section, powder etc.) by crystallization with functional group's terminal group, small molecule monomer and catalyzer enrichment in the pars amorpha, molecular balance is moved to positive dirction; By the decompression or rare gas element with reaction system small molecular product H 2O takes away, so that molecular chain continues to increase, obtains the product of higher molecular weight.The solid state polymerization of poly(lactic acid) depends on the competition of chemical reaction and physical diffusion two aspects simultaneously, diffuses into Decompression atmosphere or atmosphere of inert gases through reversible chemical reaction, small molecules product from intraparticle diffusion to particle surface and then from particle surface.Determine principle according to low speed, the speed of reaction of whole polyreaction was determined by a slowest above-mentioned step.Polymerization time, polymerization temperature, catalyzer, vacuum tightness or inert gas flow, performed polymer degree of crystallinity, performed polymer geometrical shape etc. all will affect the process of solid-phase polymerization.
The fusing point of the poly(lactic acid) that employing direct method melting+solid state polymerization makes is not high, and the polymerization time of the polymerization technique that adopts is long yet up to the present.
Current direct polymerization mainly adopt tin compound as catalyzer or adopt tin compound with the sulfonic acid that only contains a sulfonic acid group as composite catalyst.Tin compound mainly is glass putty, tin protoxide, tin protochloride and stannous octoate.Sulfonic acid mainly contains tosic acid and methylsulfonic acid.
Ajioka etc. (Bull Chem Soc Jpn.68,2125,1995) have investigated nearly 20 kinds of metallic elements to the katalysis of lactic acid melt polymerization, found that to only have the catalytic effect of tin compound more remarkable.Definite says, only has the poly(lactic acid) that could obtain high molecular when adopting tin and Bivalent Tin compound (tin protoxide, tin protochloride) after long-time polymerization.But the fusing point of products therefrom lower (163 ℃) is than low 5-7 ℃ of the fusing point of ring-opening polymerization products therefrom.
Japanese Patent P3436894 discloses tosic acid and tin protochloride and has been used as composite catalyst when coming the polymerization of catalysis lactic acid, can suppress significantly the coloring phenomenon that occurs in the polymerization process, thereby obtains the polymerisate of excellent quality.Kimura etc. (Polymer, 42,5059,2001) adopt tin protochloride/tosic acid as composite catalyst, have obtained the poly(lactic acid) of high molecular by melting/solid state polymerization technique.
Although adopt tin compound can obtain the poly(lactic acid) of high molecular as catalyzer or tin compound as composite catalyst with the sulfonic acid that only contains a sulfonic acid group, but for guaranteeing that polymerization velocity was unlikely to low, it is long that polymerization time is unlikely to, and generally all has to use larger catalyzer dosage.Such as (Polymer such as Kimura, 42,5059,2001) adopt the stannous chloride dihydrate (with respect to the lactic acid polymer) of 0.4wt% in the report, be converted into mol ratio [LA]/[Sn] of lactic acid monomer unit LA and tin atom Sn, then [LA]/[Sn]≤778.But being added in when guaranteeing polymerization velocity of a large amount of metal catalysts also aggravated side reaction (such as racemization, degraded etc.), thereby caused the fusing point of products therefrom not high, the low and color and luster of thermal stability deteriorated.Only contain a sulfonic acid group sulfoacid compound although add, such as methylsulfonic acid, ethyl sulfonic acid or tosic acid, can improve to a certain extent the color and luster of product and improve to a certain extent the fusing point of product, but the poor problem of the thermal stability of product still is not resolved.
Summary of the invention
The objective of the invention is provides a kind of sulfonic acid and organic phosphorus compound of containing, the poly (lactic acid) composition with advantages such as high thermal stability, high hydrolysis resistance performance and good color and lusters for the equal relatively poor problem of the resistance toheat of poly(lactic acid) and anti-hydrolytic performance.
Another object of the present invention is for the high problem of present stage poly(lactic acid) production cost, and a kind of method of utilizing dibasic sulfoacid or polybasic sulfoacid to make catalyzer or promotor synthesizing polylactic acid is provided.Preparing poly(lactic acid) by present method, to have a polymerization velocity fast, and products therefrom has high fusing point, good color and luster and the excellent advantages such as thermostability simultaneously.
Purpose of the present invention can reach by following measures:
Poly (lactic acid) composition
A kind of poly (lactic acid) composition, contain poly(lactic acid), sulfoacid compound and organic phosphorus compound in this poly (lactic acid) composition, wherein sulfoacid compound is selected from one or more in the salt of salt, polybasic sulfoacid, polybasic sulfoacid of dibasic sulfoacid, dibasic sulfoacid, and organic phosphorus compound is selected from one or more in fatty compounds, aromatics or the heterogeneous ring compound that contains phosphorus atom.Contained dibasic sulfoacid refers to contain in the molecular formula two sulfonic group (SO in this composition 3H) a large compounds; Polybasic sulfoacid refers to contain in the molecular formula sulfonic group (SO more than three or three 3H) a large compounds.In addition, the present invention has no particular limits for their molecular structure.
The salt of the dibasic sulfoacid in this composition, the salt of polybasic sulfoacid are selected from dibasic sulfoacid, polybasic sulfoacid and contain oxygen, nitrogen, phosphorus or sulfur organic and one or more of the salt that comes, but the salt of preferred dibasic sulfoacid, polybasic sulfoacid and phosphorus-containing matter.Can directly in composition, add salt, also can add respectively dibasic sulfoacid, polybasic sulfoacid and phosphorus-containing matter and form salt to composition and in composition.
The volatility of sulfoacid compound does not have the impact of matter to the performance of composition, brings variety of issue man-hour but consider that high volatile volatile may add at composition molding, with nonvolatile dibasic sulfoacid, polybasic sulfoacid or their salt for well.For organic volatility, academicly, industrial and legally various definitions is arranged and do not have a strict difinition unification or general.So be necessary in the present invention non-volatile sulfonic acid is described.In the present invention difficult or non-volatile dibasic sulfoacid, polybasic sulfoacid refer to preparation process be over after in composition its residual rate R% by element sulphur greater than 50% dibasic sulfoacid, polybasic sulfoacid.Be more preferably residual rate R% and be not less than 70%.Specific definition to residual rate R% elaborates in the aft section of invention again.
This composition has no particular limits the type of dibasic sulfoacid, polybasic sulfoacid, can be aromatic dibasic sulfoacid, aromatic polybasic sulfoacid, it also can be the polybasic sulfoacid of aliphatic dibasic sulfoacid, aliphatics family, preferred nonvolatile aliphatic dibasic sulfoacid, polybasic sulfoacid or their salt, refer to subsequently various sulfonic acid in this restriction about " nonvolatile aliphatics ", but not only limit nonvolatile binary aliphatic sulfonic acid, i.e. nonvolatile binary aliphatic sulfonic acid, nonvolatile aliphatics polybasic sulfoacid or their salt.To the restriction that has nothing special of the carbonatoms in their molecular formula, but consider consistency with poly(lactic acid), then in their molecular formula number of carbon atom take 1-50 as well, be more preferably 1-30, best be 1-12.
The content of dibasic sulfoacid, polybasic sulfoacid is pressed sulfonate radical-SO in this composition 3The quality meter of the sulphur atom among the H (does not comprise 0 with 0-10000ppm, such as 10ppm～10000ppm) for well, be preferably 0-8000ppm (not comprising 0), 10-6000ppm more preferably, 100-5000ppm more preferably, 200-4000ppm more preferably is preferably 300-3000ppm again.Content is too small, then is difficult to guarantee its thermostability; The too high mechanical property that then can affect polyester.
Contained aromatic dibasic sulfoacid, the aromatic polybasic sulfoacid of this composition can be the benzene disulfonic acid of benzene disulfonic acid, the many sulfonic acid of benzene, replacement or the many sulfonic acid of benzene of replacement; Also can be the naphthalene disulfonic acid of naphthalene disulfonic acid, the many sulfonic acid of naphthalene, replacement or the many sulfonic acid of naphthalene of replacement.But be preferably benzene disulfonic acid, naphthalene disulfonic acid.
This composition is for having molecular formula HO 3S-R-SO 3The dibasic sulfoacid of H, R is preferably the alkylidene group of C1-C30, the cycloalkylidene of C3-C30, the alkylene group of C3-C30, the inferior alkynyl group of C4-C30, the inferior alkynyl group of the replacement of the replacement cycloalkylidene of the substituted alkylene of C1-C30, C3-C30, the replacement alkylene group of C3-C30 or C4-C30; Specifically, R can be methylene radical, ethylidene, the propylidene of straight or branched, the butylidene of straight or branched, the pentylidene of straight or branched, the hexylidene of straight or branched, the inferior heptyl of straight or branched, straight or branched octylene, straight or branched nonamethylene, the inferior decyl of straight or branched, the inferior decyl of straight or branched, the inferior undecyl of straight or branched, the inferior dodecyl of straight or branched, the inferior tridecyl of straight or branched, the inferior tetradecyl of straight or branched, the inferior pentadecyl of straight or branched, the inferior hexadecyl of straight or branched, the inferior heptadecyl of straight or branched, the inferior octadecyl of straight or branched, the inferior nonadecyl of straight or branched, the perhaps inferior eicosyl of straight or branched; R also can be the substituted alkylene that contains at least one alkyl, cycloalkyl, amino, hydroxyl, alkoxyl group, carboxyl, ester group, acyl group, aldehyde radical, amide group, itrile group, nitro or halogen group; R also can be the cycloalkylidene of C3-C30 or the cycloalkylidene of replacement; R also can be the alkylene group that the alkylene group of the ethylene linkage C3-C30 that is in any position or the ethylene linkage that replaces are in the C3-C30 of any position.R can also be that acetylene bond is in the inferior alkynyl group of C4-C30 of any position or the acetylene bond that replaces is in the inferior alkynyl group of C4-C30 of any position.
This composition is for having molecular formula HO 3S-R-SO 3The dibasic sulfoacid of H, R are preferably the alkylidene group of C1-C12.That is to say, dibasic sulfoacid preferred be methylene-sulfonic acid, ethionic acid, the third disulfonic acid, fourth disulfonic acid, penta disulfonic acid, own disulfonic acid, heptan disulfonic acid, hot disulfonic acid, the ninth of the ten Heavenly Stems disulfonic acid, the last of the ten Heavenly stems disulfonic acid, 1,11-undecane disulfonic acid or 1,12-dodecane disulfonic acid.Better be the third disulfonic acid, fourth disulfonic acid, penta disulfonic acid, own disulfonic acid.The alkylidene group of C3-C6 more preferably.Best is the third disulfonic acid, fourth disulfonic acid.
This composition has no particular limits the polybasic sulfoacid molecular structure, and what restriction its molecular weight is not had yet.But consider the consistency of they and monomer, oligopolymer and polyester, then in the molecular formula of polybasic sulfoacid the number of carbon atom take 3-50 as well, be more preferably 3-20, best be 3-12.Polybasic sulfoacid molecular formula R ' (SO 3H) alkylidene of the preferred C3-C20 of R ', the inferior cycloalkyl of C3-C20, the inferior alkenyl of C4-C20, the inferior alkynyl group of C5-C20 among the n, the replacement time alkenyl of the replacement alkylidene of C3-C20, the replacement of C3-C20 time cycloalkyl, C4-C20 or the replacement time alkynyl group of C5-C20.Polybasic sulfoacid R ' (SO specifically 3H) among the n (n is not less than 3 integer), R ' can be propylidyne, the butylidyne of straight or branched, the pentylidyne of straight or branched, the hexylidyne of straight or branched, the inferior heptyl of straight or branched, the inferior octyl group of straight or branched, the inferior nonyl of straight or branched, the inferior decyl of straight or branched, the inferior decyl of straight or branched, the inferior undecyl of straight or branched, the inferior dodecyl of straight or branched, the inferior tridecyl of straight or branched, the inferior tetradecyl of straight or branched, the inferior pentadecyl of straight or branched, the inferior hexadecyl of straight or branched, the inferior heptadecyl of straight or branched, the inferior octadecyl of straight or branched, the inferior nonadecyl of straight or branched, the perhaps inferior eicosyl of straight or branched; R ' also can be the replacement alkylidene that contains at least one alkyl, cycloalkyl, amino, hydroxyl, alkoxyl group, carboxyl, ester group, acyl group, aldehyde radical, amide group, itrile group, nitro or halogen group; R ' also can be the inferior cycloalkyl of C3-C20 or the inferior cycloalkyl of replacement; R ' also can be the inferior alkenyl that the inferior alkenyl of the ethylene linkage C4-C20 that is in any position or the ethylene linkage that replaces are in the C4-C20 of any position.R ' can also be that acetylene bond is in C5-C20 alkynyl group of any position or the acetylene bond that replaces is in C5-C20 alkynyl group of any position.
This composition is R ' (SO to molecular formula 3H) 3Polybasic sulfoacid in the alkylidene that most preferably is C3-C20 of R '.Be preferably the alkylidene of C3-C12.
Organic phosphorus compound in this composition is selected from one or more in fatty compounds, aromatics or the heterogeneous ring compound that contains phosphorus atom, the restriction of above-mentioned " containing phosphorus atom " is not only to refer to fat and compounds of group, and refer to thereafter each compound, namely contain phosphorus atom fatty compounds, contain phosphorus atom aromatics, contain the heterogeneous ring compound of phosphorus atom.Above-mentioned organic phosphorus compound can be comprised of one or more the fatty compounds that contains phosphorus atom, also can be formed by one or more phosphorous aromatics, also can be formed by one or more phosphorus hetercyclic compound, can also jointly be formed by two or more the combination in above-mentioned three kinds of compounds.
Wherein phosphorous heteroatomic heterogeneous ring compound can be for containing the furan derivatives of phosphoric, thiazole derivative, thiophene derivant, imdazole derivatives, pyridine derivate, pyridazine derivatives, pyrimidine derivatives, pyrazines derivatives and purine derivative, be specifically as follows adenine phosphate, mephosfolan, isoxathion, methylpyridine phosphorus, Pyrimithate, lythidathion, pririmiphos_methyl, 1-butyl-3-Methylimidazole dibutyl phosphate salt, three (2-furyl) phosphine, three (2-thienyl) phosphine, three (4-morpholino) phosphine, diphenyl-2-pyridyl phosphine is preferably methylpyridine phosphorus, Pyrimithate, lythidathion, pririmiphos_methyl.The present invention is to the restriction that has nothing special of the carbonatoms in the fatty compounds that contains phosphorus, but considers the consistency of polyester, then in their molecular formula number of carbon atom with 1-40 for well, be more preferably 1-30; Phosphorous fatty compounds can be trimethyl phosphite 99, triethyl phosphate, the tricresyl phosphate propyl ester, tributyl phosphate, the tricresyl phosphate tert-butyl ester, trioctyl phosphate, dimethyl phosphate, diethyl phosphoric acid, dioctylphosphoric acid ester, DCP, trimethyl phosphite, triethyl-phosphite, the tricresyl phosphite isopropyl ester, tributyl phosphate, tricresyl phosphite isodecyl ester, dimethylphosphite, diethyl phosphite, phosphorous acid diisopropyl fat, di-n-butyl phosphite, tri isopropyl phosphorite, tetraisopropyl methylene diphosphate, the triallyl phosphoric acid ester, vinyl phosphate, 3-[three (methylol) phosphorus base] propionic ester, tricresyl phosphate (2, the 3-dibromopropyl) ester, triethyl oxygen six phosphoric acid salt, the triethyl bisphosphate, tricresyl phosphate (butoxyethyl group) ester, the ethylidene pyrodust, trimethylammonium phosphorus, triethyl phosphine, the tripropyl phosphine, tri isopropyl phosphine, tributylphosphine, three tertiary butyl phosphines, tricyclohexyl phosphine, tri-n-octyl phosphine, three normal-butyl phosphine oxides, three cyclopentyl phosphines, trioctylphosphine, 3-phosphonate group propionic acid, trimethyl phosphono acetate, trimethylammonium phosphono formate, phosphono propionic acid triethyl, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, the acetonyl diethyl phosphonate, two (diphenylphosphine) methane, 1,2-(diphenylphosphine) ethane, 1,5-(diphenylphosphine) pentane, 1,6-(diphenylphosphine) hexane; Be preferably trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, the tricresyl phosphate tert-butyl ester.Phosphorous aromatics can be triphenyl phosphorus, the triphenylphosphine polymkeric substance, diphenylphosphine, three p-methylphenyl phosphorus, triphenylphosphinc oxide, triphenylphosphate, triphenyl phosphite, tritolyl phosphate, di(2-ethylhexyl)phosphate cresols ester, three (p-nitrophenyl) phosphoric acid ester, 1-naphthalene phosphoric acid, three pairs of toluene phosphoric acid ester, three (2, the 4-di-t-butyl) phenyl-phosphite, three (2, the 6-Dimethoxyphenyl) phosphorus, diphenyl 2 ethylhexyl phosphate, paraoxon, tricresyl phosphate (m-tolyl ester), three (2, the 4-di-t-butyl) phenyl-phosphite, 2-(di-t-butyl phosphine) biphenyl, three (2-tolyl) phosphine, 1, two (diphenyl phosphine) butane of 4-, two (diphenyl phosphine) propane of 1,3-, three basic Phenylphosphines, 1-triphenylphosphine-2-acetone, the allyl group diphenylphosphine, three (4-methoxyphenyl) phosphorus, diethyl phenyl phosphine, the ethyl diphenylphosphine, isopropyl diphenyl base phosphine, the phenyl dicyclohexylphosphontetrafluoroborate, diphenylcyclohexyl phosphine, phenylbenzene methoxy base phosphine, phenylbenzene oxyethyl group phosphine; Be preferably triphenylphosphate, triphenyl phosphite.
The content of above-mentioned organic phosphorus compound in composition is counted with 0-200000ppm (not comprising 0) as well with the quality of phosphorus atom, is preferably 0-100000ppm (not comprising 0), and more preferably 10-80000ppm is preferably 10-10000ppm.Content is too small, the situation of its hydrolytic resistance may occur being difficult to guarantee; The too high mechanical property that then may affect polyester.The mol ratio of organic phosphorus compound and two, polybasic sulfoacid has comparatively significantly impact to the anti-hydrolytic performance of composition.The too high then composition of mol ratio might be met water and is alkalescence, promotes the hydrolysis of poly(lactic acid); Otherwise mol ratio is crossed low then composition and might be met water and be acid, promotes equally the hydrolysis of poly(lactic acid).Therefore, the mole number of the phosphorus atom in the organic phosphorus compound and the mole number of the sulphur atom in the sulfoacid compound than generally with between 0.1 to 10 for good, be preferably 0.5～6.
Poly (lactic acid) composition of the present invention has good anti-hydrolytic performance: when processing 5 days under 60 ℃, the condition of relative humidity 90%, the fall of the weight-average molecular weight of poly(lactic acid) is no more than 50%.Better be no more than 30%, best is no more than 10%.
This composition also has higher thermostability simultaneously.Be under 200 ℃ the condition in temperature, its thermal weight loss speed (instant heating degradation rate) is less than 0.1wt%/min, better less than 0.05wt%/min, in the time of preferably less than 0.005wt%.To measure composition by thermal gravimetric analyzer (TGA) be that Isothermal Hot weight loss rate under 200 ℃ the condition is estimated in temperature to thermostability among the present invention.Measure and generally carry out under the constant speed inert gas, rare gas element can be air, nitrogen, argon gas, helium etc., but preferred nitrogen.The flow velocity of inert gas is generally take 20-200ml/min as good, preferred 60-120ml/min, and that best is 100ml/min.
This composition is not particularly limited the characteristic of poly(lactic acid).But in order to obtain high heat resistance with poly(lactic acid), the preferred high poly(lactic acid) of optical purity.More preferably in total lactic component, contain L body or D body more than 80 % by mole, further preferably contain more than 90 % by mole, particularly preferably contain L body or D body more than 95 % by mole.On be limited to 100 % by mole.
In addition, the poly(lactic acid) in this composition from the viewpoint of thermotolerance, forming process, is preferably used the polylactic acid stereoscopic complex compound.As the method for making the polylactic acid stereoscopic complex compound, can list: be more than 90 % by mole with the L body, preferred more than 95 % by mole, more preferably the poly (l-lactic acid) more than 98 % by mole and D body are more than 90 % by mole, be preferably more than 95 % by mole, more preferably the poly-D-ALPHA-Hydroxypropionic acid more than 98 % by mole is by melting mixing or the solution method of mixing such as mixing.In addition, can also list the method that Pfansteihl and poly-D-ALPHA-Hydroxypropionic acid is formed segmented copolymer.From the viewpoint of easy formation polylactic acid stereoscopic complex compound, preferably make poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid segmented copolymer.
The molecular weight of poly(lactic acid), molecular weight distribution, as long as in fact can forming process, just there is no particular limitation, as weight-average molecular weight, from stable on heating viewpoint, preferred more than 1,000, more preferably more than 2,000, further preferred more than 5,000, particularly preferably more than 10,000, most preferably more than 30,000.The upper limit is not particularly limited, but from the viewpoint of flowability, preferred 500,000 below, more preferably below 300,000, further preferred below 200,000.Particularly, from obtaining having the viewpoint of excellent stable on heating resin combination, weight-average molecular weight is preferably in 0.5 ten thousand-300,000 scope.To the fusing point of aliphatic polyester, there is no particular limitation, from the viewpoint of thermotolerance (heat-drawn wire), is preferably more than 90 ℃, more preferably more than 150 ℃.
Poly (lactic acid) composition of the present invention can only be comprised of above-mentioned poly(lactic acid), sulfoacid compound and organic phosphorus compound.Also can in the scope of not damaging purpose of the present invention, also contain other one or more stablizers.Can use the stablizer of common thermoplastic resin.Specifically can enumerate, antioxidant, photostabilizer, formaldehyde are supplied agent, formic acid is supplied agent etc., but can preferably use antioxidant and photostabilizer.
As the antioxidant that uses among the present invention, can enumerate sterically hindered phenol based compound, bi-ester of phosphite, sulfide compound etc.Example as the sterically hindered phenol based compound; can enumerate; Octadecane base-3-(3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester; Octadecane base-3-(3 '-methyl-the 5 '-tertiary butyl-4 '-hydroxy phenyl) propionic ester; n-tetradecane base-3-(3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester; 1; 6-hexylene glycol-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 1; 4-butyleneglycol-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2; 2 '-methylene-bis-(4-methyl-tert-butyl phenol); triethylene glycol-two-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl)-propionic ester]; four [methylene radical-3-(3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane; 3; 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1; the 1-methylethyl] 2; 4; 8; 10-four oxaspiros (5; 5) undecane; N; N '-two-3-(3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionyl hexamethylene-diamine; N; N '-tetramethylene-two-3-(3 '-methyl-the 5 '-tertiary butyl-4 '-hydroxyl phenol) propionyl diamines; N; N '-two-[3-(3; 5-di-t-butyl-4-hydroxyl phenol) propionyl] hydrazine; N-salicylyl-N '-salicylidene hydrazine; 3-(N-salicylyl) amino-1; 2; the 4-triazole; N; N '-two [2-{3-(3,5-di-tert-butyl-hydroxy phenyl) propionyloxy } ethyl] oxyamide etc.Preferably, triethylene glycol-two-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl)-propionic ester] and four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane.As the phosphorous acid ester based compound, preferably at least 1 P-O bond is incorporated into the compound on the aromatic series base, as concrete example, can enumerate, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, four (2, the 4-di-tert-butyl-phenyl) 4,4 '-Ya biphenyl phosphinate, two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane-two-phosphorous acid ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-two-phosphorous acid ester, 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, 4,4 '-butylidene-two (3-methyl-6-tert butyl phenyl-two-tridecyl) phosphorous acid ester, 1,1,3-three (2-methyl-4-double tridecyl phosphorous acid ester-5-tert-butyl-phenyl) butane, three (mixing single and two-nonyl phenyl) phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, 4, the different base of 4 '-Ya two (phenyl-dialkyl phosphites) etc., what can preferably use then is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2, the inferior different base two (4 of 2-, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-two-phosphorous acid ester, four (2, the 4-di-tert-butyl-phenyl) 4,4 '-biphenylene phosphorous acid ester etc.
Concrete example as the thioether based compound, can enumerate dilauryl thiodipropionate, two-tridecyl thiodipropionate, myristyl thiodipropionate, two octadecyl thiodipropionate, tetramethylolmethane-four (3-lauryl thiopropionate), tetramethylolmethane-four (3-dodecyl thiopropionate), tetramethylolmethane-four (3-octadecyl thiopropionate), tetramethylolmethane-four (3-myristyl thiopropionate), tetramethylolmethane-four (the hard ester acyl of 3-thiopropionate) etc.
As the photostabilizer that uses among the present invention, can enumerate benzophenone based compound, benzotriazole based compound, aromatic series benzoic ether based compound, oxalic acid aniline based compound, cyanoacrylate based compound and bulky amine based compound etc.Concrete example as the benzophenone based compound, can enumerate, benzophenone, 2,4-dihydro benzophenone, 2,2 ', 4,4 '-tetrahydro-benzophenone, ESCALOL 567,2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, 2,2 '-dihydroxy benaophenonel, 2-hydroxyl 4-octyloxy benzophenone, 2-hydroxyl-4 dodecyl benzophenone, 2-hydroxyl-4-methoxyl group-5-diphenylsulfone ketone, 5-chlorine-2-hydroxyl benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-5-diphenylsulfone ketone, 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone, 2-hydroxyl-4-(2-hydroxy-3-methyl-acryloxy isopropoxy benzophenone etc.
Concrete example as the benzotriazole based compound, can enumerate, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl)-the 2H-benzotriazole, 2-(2 '-hydroxyl-3,5 '-di-t-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl-5 '-methyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl-phenyl)-5-chloro-benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two uncle's isopentyl-phenyl) benzotriazole, (2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-[2 '-hydroxyl-3 ', 5 '-two (α, α-dimethylbenzyl) phenyl] benzotriazole, 2-[2 '-hydroxyl-3 ', 5 '-two (alpha, alpha-dimethylbenzyl) phenyl]-the 2H-benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole etc.
As the concrete example of aromatic series phenylformic acid based compound, can enumerate the alkyl phenyl salicylate classes such as p-tert-butyl-phenyl salicylate, p-octyl phenyl salicylate.
As the concrete example of oxalic acid amino benzenes compounds, can enumerate 2-oxyethyl group-2 '-ethyl oxalic acid dianiline, the 2-oxyethyl group-5-tertiary butyl-2 '-ethyl oxalic acid dianiline, 2-oxyethyl group-3 '-dodecyl oxalic acid dianiline etc.
As the concrete example of cyanoacrylate based compound, can enumerate ethyl-2-cyano group-3,3 '-phenylbenzene-acrylate, 2-ethylhexyl-2-cyano group-3,3 '-phenylbenzene-acrylate etc.
As the concrete example of bulky amine based compound, can enumerate 4-acetoxyl group-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6,6-tetramethyl piperidine, 4-acryloxy-2,2,6,6-tetramethyl piperidine, 4-(phenylacetyl oxygen base)-2,2,6,6-tetramethyl piperidine, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine, 4-methoxyl group-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6, the 6-tetramethyl piperidine, 4-cyclohexyloxy-2,2,6, the 6-tetramethyl piperidine, 4-benzyloxy-2,2,6,6-tetramethyl piperidine, 4-phenoxy group-2,2,6,6-tetramethyl piperidine, 4-(ethylamino methanoyl)-2,2,6, the 6-tetramethyl piperidine, 4-(cyclohexyl carboxyamide oxygen base)-2,2,6, the 6-tetramethyl piperidine, 4-(phenyl amino methanoyl)-2,2,6,6-tetramethyl piperidine, two (2,2,6,6-tetramethyl--4-piperidyl)-carbonic ether, two (2,2,6,6-tetramethyl--4-piperidyl)-barkite, two (2,2,6,6-tetramethyl--4-piperidyl)-malonic ester, two (2,2,6,6-tetramethyl--4-piperidyl)-sebate, two (2,2,6,6-tetramethyl--4-piperidyl)-adipic acid ester, two (2,2,6,6-tetramethyl--4-piperidyl)-terephthalate, 1,2-two (2,2,6,6-tetramethyl--4-piperidyl oxygen)-ethane, α, α '-two (2,2,6,6-tetramethyl--4-piperidyl oxygen)-p-dimethylbenzene, two (2,2,6,6-tetramethyl--4-piperidyl cresylene-2, the 4-diurethanes, two (2,2,6,6-tetramethyl--4-piperidyl)-hexa-methylene-1, the 6-diurethanes, three (2,2,6,6-tetramethyl--4-piperidyl)-benzene-1,3,5-tricarboxylic ester, three (2,2,6,6-tetramethyl--4-piperidyl)-and benzene-1,3, the 4-tricarboxylic ester, 1-[2-{3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy }-butyl]-4-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy } 2,2,6, the 6-tetramethyl piperidine, 1,2,3,4-BTCA and 1,2,2,6,6-pentamethyl--4-piperidine alcohols and β, β, β ', β '-tetramethyl--3,9-[2,4,8,10-, four oxaspiros (5,5) undecane] condenses etc. of ethylene glycol.
In poly (lactic acid) composition of the present invention, in the scope of not damaging purpose of the present invention, can also contain nucleator, weather resisting agent, lubricant, releasing agent, fire retardant, dyestuff, antistatic agent, whipping agent etc.
In poly (lactic acid) composition of the present invention, in the scope of not damaging purpose of the present invention, can also contain other thermoplastic resins, as: polyamide resin, polyphenylene sulfide, polyether-ether-ketone resin, polysulfone resin, polyethersulfone resin, polycarbonate resin, polyimide resin, fluoro-resin, polyvinyl chloride (PVC) RESINS, alicyclic vinyl resinoid, cellulose acetate resin, polyvinyl alcohol resin etc.; Or thermosetting resin, as: resol, ethyl-amine resin, Resins, epoxy, silicone resin etc.
In the present invention, the composition of gained can carry out moulding by the personnel's such as known injection molding, extrusion moulding, blow molding method, is widely used as the products formed of arbitrary shape.Products formed refer to film, thin slice, fiber, fabric, non-woven fabrics, injection-molded article, extrusion molding article, moulded section product, blow molding product or with complex body of other materials etc.Can be used for automotive interior part, automobile exterior parts, TV part, air supply rate, fly-ash separator parts, refrigerator parts, phone parts, facsimile recorder parts, camera components, timepiece, computer part, printer unit, copier part, bathroom product parts, civil material and parts, agricultural materials and parts thereof, gardening material and parts, fishery with material and parts, articles for daily use material and parts thereof, and other Application Areass.Products formed also can after further processing (such as coating, plating etc.), re-use in addition.
This polymer blend that has simultaneously good hydrolytic resistance, excellent thermal and good color and luster among the present invention, its preparation method is had no particular limits, can obtain by in poly lactic acid polymerized process, adding organic phosphorus compound, also can be by in the poly(lactic acid) product, adding organic phosphorus compound.The adding method of the organic phosphorus compound among the present invention also has no particular limits, and can adopt the melting mixing method, also can adopt solution mixing method, can also adopt the method for twin screw blend.
The preparation method of poly (lactic acid) composition
The invention discloses a kind of in the process of acid through direct polycondensation by lactic, add sulfonic acid and organic phosphorus compound or containing in the poly(lactic acid) of sulfonic acid add the method that the organic phosphorus compound preparation contains the poly (lactic acid) composition of sulfoacid compound and organic phosphorus compound.
The polymerization process of poly(lactic acid) direct condensation can be melting mass polymerization, solid state polymerization or their combination.Provide a kind of better method at this, namely by melt polymerization and solid state polymerization in conjunction with or formed by melt polymerization separately, its concrete steps are as follows:
Melt polymerization: under the inert gas or pressure be in the decompression situation of 50～0.1KPa, add dibasic sulfoacid and/or polybasic sulfoacid and as catalyzer lactic acid monomer or its oligopolymer carried out melt phase polycondensation 2～30h.
Solid state polymerization: the polyester prepolyer that melt phase polycondensation is obtained after crystallization treatment, under inert gas or pressure be to carry out 2～100 hours solid state polymerizations in the decompression situation of 0.05～2KPa.
The dibasic sulfoacid as catalyzer in the method for preparing poly (lactic acid) composition of the present invention can be a kind of dibasic sulfoacid, also can be the mixture of two or more dibasic sulfoacids; In like manner, polybasic sulfoacid can be a kind of polybasic sulfoacid, also can be the mixture of two or more polybasic sulfoacids.The mixture of dibasic sulfoacid and polybasic sulfoacid can be one or more dibasic sulfoacid and the mixture of one or more polybasic sulfoacid.
In the aforesaid method, organic phosphorus compound can add in the melt polymerization system simultaneously with dibasic sulfoacid, polybasic sulfoacid, also can after finishing, melt polymerization add in the poly(lactic acid), can also after finishing, solid state polymerization join in the solid state polymerization product, be that the method for preparing poly (lactic acid) composition among the present invention is made catalyzer with dibasic sulfoacid and/or polybasic sulfoacid, carry out melt phase polycondensation, obtain the poly(lactic acid) product; Also can further the melt phase polycondensation product be carried out solid-phase polymerization, obtain poly-lactic acid in high molecular weight; Organic phosphorus compound can add when melt polymerization begins in the lactic acid monomer, also can add after melt polymerization finishes in the poly(lactic acid), can also add in the poly(lactic acid) after solid state polymerization finishes.In more detail, the present invention can be divided into following three kinds of methods substantially:
Method one may further comprise the steps:
A: under inert gas or pressure be in the decompression situation of 50～0.1KPa, add organic phosphorus compound when adding dibasic sulfoacid or polybasic sulfoacid as catalyzer after, lactic acid monomer or its oligopolymer are carried out melt phase polycondensation 2～30h;
B: the poly(lactic acid) prepolymer that melt phase polycondensation obtains after crystallization treatment, under inert gas or pressure be to carry out 2～100 hours solid state polymerizations in the decompression situation of 0.05～2KPa.
Method two may further comprise the steps:
A: under inert gas or pressure be in the decompression situation of 50～0.1KPa, add dibasic sulfoacid or polybasic sulfoacid and as catalyzer lactic acid monomer or its oligopolymer carried out melt phase polycondensation 2～30h;
B: add behind the organic phosphorus compound poly(lactic acid) prepolymer crystallization treatment;
C: with prepolymer under the inert gas or pressure be to carry out 2～100 hours solid state polymerizations in the decompression situation of 0.05～2KPa.
Method three comprises following steps:
A: under inert gas or pressure be in the decompression situation of 50～0.1KPa, add dibasic sulfoacid or polybasic sulfoacid and as catalyzer lactic acid monomer or its oligopolymer carried out melt phase polycondensation 2～30h;
B: the poly(lactic acid) prepolymer that melt phase polycondensation obtains after crystallization treatment, under inert gas or pressure be to carry out 2～100 hours solid state polymerizations in the decompression situation of 0.05～2KPa;
C: in the solid state polymerization product, add organic phosphorus compound.
The restriction of each material in the aforesaid method below is described further for method as mentioned above.
Among the preparation method of the present invention, as the dibasic sulfoacid of catalyzer or the volatility of polybasic sulfoacid effect of the present invention do not had substantial impact.But the too high meeting of the volatility of dibasic sulfoacid or polybasic sulfoacid brings following three problems:
A. because the time of polyester is generally longer, the too high meeting of volatility causes the decay of catalytic activity too fast, affects polymerization velocity;
B. to guarantee that polymerization velocity need to add a large amount of catalyzer, increase the cost of polymerization;
C. because sulfonic acid is strong acid, high-volatile dibasic sulfoacid or polybasic sulfoacid are had higher requirement to the erosion resistance of whole paradigmatic system as catalyzer.
In view of this, among the present invention take difficult volatility or non-volatility dibasic sulfoacid or polybasic sulfoacid as catalyzer as good.For organic volatility, academicly, industrial and legally various definitions is arranged and do not have a strict difinition unification or general.So be necessary in the present invention non-volatile sulfonic acid is described.In the present invention difficult or non-volatile dibasic sulfoacid, polybasic sulfoacid refer to polymerization be over after in polyester product its residual rate R% by element sulphur greater than 50% dibasic sulfoacid, polybasic sulfoacid.If do not contain other additives that do not add sulfur-bearing in element sulphur and the polymerization process in the polymerization single polymerization monomer, then the residual rate of dibasic sulfoacid or polybasic sulfoacid is defined by formula (1):
R % = m sp m s 0 × 100 % - - - ( 1 )
M in the formula S0Be the catalyzer dibasic sulfoacid of polymerization process interpolation, the sulfonate radical-SO of polybasic sulfoacid origin 3The quality of the element sulphur among the H; m SpQuality for the element sulphur of sulfonate radical origin in the polyester product.
If under an element sulphur form with sulfonate radical existed in dibasic sulfoacid, the polybasic sulfoacid, then formula (1) can be expressed as:
R % = m p · C sp m 0 · C s 0 × 100 % - - - ( 2 )
Wherein: m 0And m pThe quality of products therefrom after the monomer mass that drops into when being respectively polymerization and the polymerization, C S0And C SpBe respectively polymerization when beginning with respect to the sulphur content in the products therefrom after the sulphur content of monomer and the polymerization.Definition observed yield Y% is:
Y % = m p m 0 × 100 % - - - ( 3 )
Variable being changed to of formula (2) then:
R % = C sp C s 0 × Y % - - - ( 4 )
With the volatile evaluation index of residual rate as dibasic sulfoacid or polybasic sulfoacid, the residual rate of dibasic sulfoacid or polybasic sulfoacid was not less than 50% as good after then this polymerization process was finished take polymerization, was more preferably and was not less than 70%.
To having no particular limits the type of dibasic sulfoacid, polybasic sulfoacid catalyzer, can be in binary aliphatic sulfonic acid, aliphatics polybasic sulfoacid, aromatic dicarboxylic sulfonic acid, the aromatic series polybasic sulfoacid one or more among this preparation method.But aromatic dicarboxylic sulfonic acid when poly lactic acid polymerized, polybasic sulfoacid acidity are stronger, easily make product painted, one or more in preferred aliphat dibasic sulfoacid, the aliphatics polybasic sulfoacid (being nonvolatile binary aliphatic sulfonic acid or nonvolatile aliphatics polybasic sulfoacid).To the restriction that has nothing special of the carbonatoms in their molecular formula.But consider the consistency of itself and poly(lactic acid), then in the molecular formula of dibasic sulfoacid the number of carbon atom take 1-50 as well, be more preferably 1-30, best be 1-12; In the molecular formula of polybasic sulfoacid the number of carbon atom take 3-50 as well, be more preferably 3-20, best be 1-12.
Add-on as dibasic sulfoacid, polybasic sulfoacid or their mixture of catalyzer among the preparation method of poly (lactic acid) composition of the present invention is pressed sulfonate radical SO 3Among the H quality meter of sulphur atom with 0ppm-20000ppm (do not comprise 0, with respect to the quality of lactic acid monomer or oligopolymer, lower with) for well, be 10-8000ppm better, be preferably again 100ppm-5000ppm, 200ppm-4000ppm more preferably, that best is 300-3000ppm.The too high degraded in mechanical properties that then easily causes product is crossed the low thermostability that then also affects product when affecting catalytic performance.
The organic phosphorus compound that adds among the preparation method of poly (lactic acid) composition of the present invention is selected from organic phosphorus compound and is selected from fatty compounds, aromatics or the heterogeneous ring compound that contains phosphorus atom one or more.The organic phosphorus compound that namely adds can be comprised of one or more phosphorous heteroatomic heterogeneous ring compound, also can be formed by one or more phosphorous fatty compounds, also can be formed by one or more phosphorous aromatics, can also jointly be formed by two or more the combination in above-mentioned three kinds of compounds.Wherein phosphorous heteroatomic heterogeneous ring compound can be for containing the furan derivatives of phosphoric, thiazole derivative, thiophene derivant, imdazole derivatives, pyridine derivate, pyridazine derivatives, pyrimidine derivatives, pyrazines derivatives and purine derivative, be specifically as follows adenine phosphate, mephosfolan, isoxathion, methylpyridine phosphorus, Pyrimithate, lythidathion, pririmiphos_methyl, 1-butyl-3-Methylimidazole dibutyl phosphate salt, three (2-furyl) phosphine, three (2-thienyl) phosphine, three (4-morpholino) phosphine, diphenyl-2-pyridyl phosphine is preferably methylpyridine phosphorus, Pyrimithate, lythidathion, pririmiphos_methyl.The present invention is to the restriction that has nothing special of the carbonatoms in the fatty compounds that contains phosphorus, but considers the consistency of polyester, then in their molecular formula number of carbon atom with 1-40 for well, be more preferably 1-30; Phosphorous fatty compounds can be trimethyl phosphite 99, triethyl phosphate, the tricresyl phosphate propyl ester, tributyl phosphate, the tricresyl phosphate tert-butyl ester, trioctyl phosphate, dimethyl phosphate, diethyl phosphoric acid, dioctylphosphoric acid ester, DCP, trimethyl phosphite, triethyl-phosphite, the tricresyl phosphite isopropyl ester, tributyl phosphate, tricresyl phosphite isodecyl ester, dimethylphosphite, diethyl phosphite, phosphorous acid diisopropyl fat, di-n-butyl phosphite, tri isopropyl phosphorite, tetraisopropyl methylene diphosphate, the triallyl phosphoric acid ester, vinyl phosphate, 3-[three (methylol) phosphorus base] propionic ester, tricresyl phosphate (2, the 3-dibromopropyl) ester, triethyl oxygen six phosphoric acid salt, the triethyl bisphosphate, tricresyl phosphate (butoxyethyl group) ester, the ethylidene pyrodust, trimethylammonium phosphorus, triethyl phosphine, the tripropyl phosphine, tri isopropyl phosphine, tributylphosphine, three tertiary butyl phosphines, tricyclohexyl phosphine, tri-n-octyl phosphine, three normal-butyl phosphine oxides, three cyclopentyl phosphines, trioctylphosphine, 3-phosphonate group propionic acid, trimethyl phosphono acetate, trimethylammonium phosphono formate, phosphono propionic acid triethyl, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, the acetonyl diethyl phosphonate, two (diphenylphosphine) methane, 1,2-(diphenylphosphine) ethane, 1,5-(diphenylphosphine) pentane, 1,6-(diphenylphosphine) hexane; Be preferably trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, the tricresyl phosphate tert-butyl ester.Phosphorous aromatics can be triphenyl phosphorus, the triphenylphosphine polymkeric substance, diphenylphosphine, three p-methylphenyl phosphorus, triphenylphosphinc oxide, triphenylphosphate, triphenyl phosphite, tritolyl phosphate, di(2-ethylhexyl)phosphate cresols ester, three (p-nitrophenyl) phosphoric acid ester, 1-naphthalene phosphoric acid, three pairs of toluene phosphoric acid ester, three (2, the 4-di-t-butyl) phenyl-phosphite, three (2, the 6-Dimethoxyphenyl) phosphorus, diphenyl 2 ethylhexyl phosphate, paraoxon, tricresyl phosphate (m-tolyl ester), three (2, the 4-di-t-butyl) phenyl-phosphite, 2-(di-t-butyl phosphine) biphenyl, three (2-tolyl) phosphine, 1, two (diphenyl phosphine) butane of 4-, two (diphenyl phosphine) propane of 1,3-, three basic Phenylphosphines, 1-triphenylphosphine-2-acetone, the allyl group diphenylphosphine, three (4-methoxyphenyl) phosphorus, diethyl phenyl phosphine, the ethyl diphenylphosphine, isopropyl diphenyl base phosphine, the phenyl dicyclohexylphosphontetrafluoroborate, diphenylcyclohexyl phosphine, phenylbenzene methoxy base phosphine, phenylbenzene oxyethyl group phosphine; Be preferably triphenylphosphate, triphenyl phosphite.
The add-on of above-mentioned organic phosphorus compound is counted with 0-200000ppm (not comprising 0) as well with the quality of phosphoric, is preferably 0-100000ppm (not comprising 0), and more preferably 10-80000ppm is preferably 10-10000ppm.Content is too small, the situation of its hydrolytic resistance may occur being difficult to guarantee; The too high mechanical property that then may affect polyester.The mol ratio of organic phosphorus compound and two, polybasic sulfoacid has comparatively significantly impact to the anti-hydrolytic performance of composition.The too high then composition of mol ratio might be met water and is alkalescence, promotes the hydrolysis of poly(lactic acid); Otherwise mol ratio is crossed low then composition and might be met water and be acid, promotes equally the hydrolysis of poly(lactic acid).Therefore, the mole number of the mole number of organic phosphorus compound origin phosphorus atom and the sulphur atom of sulfoacid compound origin than generally with between 0.1 to 20 for good, be preferably 0.5～6.
Lactic acid monomer or its oligopolymer can not done any processing in the method for preparing poly (lactic acid) composition of the present invention before polymerization; Also can be before polycondensation to the raw material pre-treatment of dewatering.Certainly, the dehydration here not only refers to the physics dehydration, also may relate to the condensation dehydration simultaneously.In this treating processes, no matter whether the existence of extra catalyst is arranged, condensation (polycondensation) may inevitably occur.
In the process of polymerization, under inert gas or in the decompression situation, add dibasic sulfoacid or polybasic sulfoacid as catalyzer with lactic acid monomer or its oligopolymer polycondensation 2～30h.The melt polymerization temperature determines by polymerization single polymerization monomer, oligopolymer and gained polyester product, for poly lactic acid polymerized temperature generally take 80-220 ℃ as good.The melt polymerization temperature is excessively low, and then polymerization velocity is low; The melt polymerization excess Temperature, then side reaction aggravation, painted intensification.Polymerization time is mainly decided on target molecular weight, but time oversize then product easy coloring, generally take 2-40 hour as good, preferred 2～30 hours.Adding to catalyzer does not have special requirement period, generally is incorporated as good after beginning with polymerization in 2 hours.By melt polymerization, the molecular weight of the poly(lactic acid) that obtains is determined by polymerizing condition, generally between several thousand to several ten thousand.The condensation of poly(lactic acid) is a reversible reaction with little equilibrium constant, and the later stage of melt condensation is because dehydration difficulty, and the rate of growth of molecular weight is very slow or do not increase, even owing to the existence of side reaction causes molecular weight and molecular weight.So generally be difficult to obtain the product of high molecular from melt condensation.
For poly(lactic acid), can adopt the molecular weight of the incompatible further raising poly(lactic acid) of solid polycondensation behind the melt polymerization.With the powder of melt polymerization product or particle through being in the decompression situation of 0.1～0.5KPa (perhaps under the inert gas) at pressure after the crystallization treatment, solid state polymerization 2～120 hours, wherein pressure progressively was down to 0.1～0.5KPa from normal pressure in 30～60 minutes.
The present invention has no particular limits the crystallization treatment of melt polymerization product.Can be that temperature with melt drops to isothermal crystal under a certain Tc, also each crystallization some time under the series of crystallization temperature; Can be crystallization under air atmosphere, under the nitrogen atmosphere, also can be crystallization under the vacuum, can also be in water or crystallization in other liquid mediums.Degree of crystallinity of the present invention also has no particular limits.Consider that from enrichment degree, inhibition particle or the powder bonded equal angles of end group then degree of crystallinity is more high better.But the too high meeting of degree of crystallinity reduces the activity of end group and reduces polymerization velocity.
The temperature of solid state polymerization determines by the second-order transition temperature of poly(lactic acid) and fusing point, that is the temperature of solid state polymerization (Ts) should be between second-order transition temperature (Tg) and fusing point (Tm):
Tg＜Ts＜Tm (5)
Be lower than second-order transition temperature, reaction can not be carried out.Being higher than fusing point then no longer is solid state polymerization.Because temperature is low, polymerization velocity is also low.To guarantee to improve polymerization temperature in the situation that particle or powder do not melt generally speaking as far as possible.Under the prerequisite greater than second-order transition temperature, preferably the temperature range of solid state polymerization be fusing point following 40 ℃ between the fusing point:
Tm-40＜Ts＜Tm (6)
Better the temperature range of solid state polymerization be fusing point following 20 ℃ between the fusing point:
Tm-20＜Ts＜Tm (7)
The temperature range of best solid state polymerization be fusing point following 10 ℃ between the fusing point:
Tm-10＜Ts＜Tm (8)
Because polymerization system molecular weight in polymerization process constantly increases, general degree of crystallinity also can improve constantly, so the fusing point of system also can constantly change in polymerization process.Fusing point can improve constantly generally speaking, and often is to improve comparatively fast at the initial stage, and the middle and later periods raising is slower even almost constant.So in polymerization process, it is constant that the temperature T s of polymerization can keep; Also can constantly change along with polymerisation run; Also can in the early stage Ts be remained on lower temperature, remain on moderate temperature mid-term and the later stage remains on comparatively high temps; Also can be in the early stage Ts be constantly adjusted and stage is constant at a certain fixed temperature etc. according to polymerisation run.
Because high molecular polymolecularity, high molecular melting has certain temperature range.So be necessary above-mentioned fusing point (or melt temperature) Tm is described.Heat-up rate when on the other hand, also being appreciated that the polymer fusing point and measuring has certain relation.Tm among the present invention refers to (10～20 ℃/min) the lower melt initiation temperature degree of measuring of medium heat-up rates.
Behind solid state polymerization, the weight-average molecular weight of poly(lactic acid) can reach more than more than ten ten thousand even 300,000.
This preparation method and the poly (lactic acid) composition that comes has good anti-hydrolytic performance: when processing 5 days under 60 ℃, the condition of relative humidity 90%, the fall of the weight-average molecular weight of poly(lactic acid) is no more than 50%.Better be no more than 30%, best is no more than 10%.
This preparation method and the poly (lactic acid) composition that comes also has higher thermostability simultaneously, under the nitrogen gas stream of 100ml/min and temperature be under 200 ℃ the condition, its thermal weight loss speed is less than 0.1wt%/min, better less than 0.05wt%/min, in the time of preferably less than 0.005wt%.
In the scope of not damaging the object of the invention, can in this polymerization process, add various auxiliary agents, as: promotor.Antioxidant, photostabilizer, painted inhibitor etc.Promotor can be metallic compound etc.Metallic compound can be alkali metal compound, alkaline earth metal compound, transistion metal compound, the compound of the metals such as rare earth compound and aluminium, gallium, indium, thallium, tin, lead and bismuth.The example of concrete metallic compound can be enumerated: lithium, potassium, barium, strontium, calcium, sodium, aluminium, titanium, manganese, samarium, zinc, chromium, gallium, iron, cadmium, indium, titanium, cobalt, tin, silver, copper, molybdenum, rubidium, caesium, zirconium, vanadium, niobium, etc. oxide compound, acetate, stearate etc.
As the antioxidant that uses among the present invention, can enumerate sterically hindered phenol based compound, bi-ester of phosphite, sulfide compound etc.Example as the sterically hindered phenol based compound; can enumerate; Octadecane base-3-(3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester; Octadecane base-3-(3 '-methyl-the 5 '-tertiary butyl-4 '-hydroxy phenyl) propionic ester; n-tetradecane base-3-(3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester; 1; 6-hexylene glycol-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 1; 4-butyleneglycol-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2; 2 '-methylene-bis-(4-methyl-tert-butyl phenol); triethylene glycol-two-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl)-propionic ester]; four [methylene radical-3-(3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane; 3; 9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1; the 1-methylethyl] 2; 4; 8; 10-four oxaspiros (5; 5) undecane; N; N '-two-3-(3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionyl hexamethylene-diamine; N; N '-tetramethylene-two-3-(3 '-methyl-the 5 '-tertiary butyl-4 '-hydroxyl phenol) propionyl diamines; N; N '-two-[3-(3; 5-di-t-butyl-4-hydroxyl phenol) propionyl] hydrazine; N-salicylyl-N '-salicylidene hydrazine; 3-(N-salicylyl) amino-1; 2; the 4-triazole; N; N '-two [2-{3-(3,5-di-tert-butyl-hydroxy phenyl) propionyloxy } ethyl] oxyamide etc.Preferably: triethylene glycol-two-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl)-propionic ester] and four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane.As the phosphorous acid ester based compound, preferably at least 1 P-O bond is incorporated into the compound on the aromatic series base, as concrete example, can enumerate, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, four (2, the 4-di-tert-butyl-phenyl) 4,4 '-Ya biphenyl phosphinate, two (2, the 4-di-tert-butyl-phenyl) tetramethylolmethane-two-phosphorous acid ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-two-phosphorous acid ester, 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, 4,4 '-butylidene-two (3-methyl-6-tert butyl phenyl-two-tridecyl) phosphorous acid ester, 1,1,3-three (the 2-methyl-4-double tridecyl phosphorous acid ester-5-tertiary butyl-phenyl) butane, three (mixing single and two-nonyl phenyl) phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, 4, the different base of 4 '-Ya two (phenyl-dialkyl phosphites) etc., what can preferably use then is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2, the inferior different base two (4 of 2-, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-two-phosphorous acid ester, four (2, the 4-di-tert-butyl-phenyl) 4,4 '-biphenylene phosphorous acid ester etc.
Concrete example as the thioether based compound, can enumerate dilauryl thiodipropionate, two-tridecyl thiodipropionate, myristyl thiodipropionate, two octadecyl thiodipropionate, tetramethylolmethane-four (3-lauryl thiopropionate), tetramethylolmethane-four (3-dodecyl thiopropionate), tetramethylolmethane-four (3-octadecyl thiopropionate), tetramethylolmethane-four (3-myristyl thiopropionate), tetramethylolmethane-four (the hard ester acyl of 3-thiopropionate) etc.
As the photostabilizer that uses among the present invention, can enumerate benzophenone based compound, benzotriazole based compound, aromatic series benzoic ether based compound, oxalic acid aniline based compound, cyanoacrylate based compound and bulky amine based compound etc.Concrete example as the benzophenone based compound, can enumerate, benzophenone, 2,4-dihydro benzophenone, 2,2 ', 4,4 '-tetrahydro-benzophenone, ESCALOL 567,2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, 2,2 '-dihydroxy benaophenonel, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4 dodecyl benzophenone, 2-hydroxyl-4-methoxyl group-5-diphenylsulfone ketone, 5-chlorine-2-hydroxyl benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-5-diphenylsulfone ketone, 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone, 2-hydroxyl-4-(2-hydroxy-3-methyl-acryloxy isopropoxy benzophenone etc.
Concrete example as the benzotriazole based compound, can enumerate, 2-(2 '-hydroxyl-5 '-methyl-phenyl)-benzotriazole, 2-(2-hydroxyl-3,5-two-uncle-amyl group phenyl)-the 2H-benzotriazole, 2-(2 '-hydroxyl-3,5 '-two-tertiary butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two-tertiary butyl-5 '-methyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two-tertiary butyl-phenyl)-5-chloro-benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two-uncle-isopentyl-phenyl) benzotriazole, (2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-[2 '-hydroxyl-3 ', 5 '-two (α, α-dimethylbenzyl) phenyl] benzotriazole, 2-[2 '-hydroxyl-3 ', 5 '-two (alpha, alpha-dimethylbenzyl) phenyl]-the 2H-benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole etc.
As the concrete example of aromatic series phenylformic acid based compound, can enumerate the alkyl phenyl salicylate classes such as p-tert-butyl-phenyl salicylate, p-octyl phenyl salicylate.
As the concrete example of oxalic acid amino benzenes compounds, can enumerate 2-oxyethyl group-2 '-ethyl oxalic acid dianiline, the 2-oxyethyl group-5-tertiary butyl-2 '-ethyl oxalic acid dianiline, 2-oxyethyl group-3 '-dodecyl oxalic acid dianiline etc.
As the concrete example of cyanoacrylate based compound, can enumerate ethyl-2-cyano group-3,3 '-phenylbenzene-acrylate, 2-ethylhexyl-2-cyano group-3,3 '-phenylbenzene-acrylate etc.
As the concrete example of bulky amine based compound, can enumerate 4-acetoxyl group-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6,6-tetramethyl piperidine, 4-acryloxy-2,2,6,6-tetramethyl piperidine, 4-(phenylacetyl oxygen base)-2,2,6,6-tetramethyl piperidine, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine, 4-methoxyl group-2,2,6,6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6, the 6-tetramethyl piperidine, 4-cyclohexyloxy-2,2,6, the 6-tetramethyl piperidine, 4-benzyloxy-2,2,6,6-tetramethyl piperidine, 4-phenoxy group-2,2,6,6-tetramethyl piperidine, 4-(ethylamino methanoyl)-2,2,6, the 6-tetramethyl piperidine, 4-(cyclohexyl carboxyamide oxygen base)-2,2,6, the 6-tetramethyl piperidine, 4-(phenyl amino methanoyl)-2,2,6,6-tetramethyl piperidine, two (2,2,6,6-tetramethyl--4-piperidyl)-carbonic ether, two (2,2,6,6-tetramethyl--4-piperidyl)-barkite, two (2,2,6,6-tetramethyl--4-piperidyl)-malonic ester, two (2,2,6,6-tetramethyl--4-piperidyl)-sebate, two (2,2,6,6-tetramethyl--4-piperidyl)-adipic acid ester, two (2,2,6,6-tetramethyl--4-piperidyl)-terephthalate, 1,2-two (2,2,6,6-tetramethyl--4-piperidyl oxygen)-ethane, α, α '-two (2,2,6,6-tetramethyl--4-piperidyl oxygen)-p-dimethylbenzene, two (2,2,6,6-tetramethyl--4-piperidyl cresylene-2, the 4-diurethanes, two (2,2,6,6-tetramethyl--4-piperidyl)-hexa-methylene-1, the 6-diurethanes, three (2,2,6,6-tetramethyl--4-piperidyl)-benzene-1,3,5-tricarboxylic ester, three (2,2,6,6-tetramethyl--4-piperidyl)-and benzene-1,3, the 4-tricarboxylic ester, 1-[2-{3-(3,5-two-tert-butyl-hydroxy phenyl) propionyloxy }-butyl]-4-[3-(3,5-two-tert-butyl-hydroxy phenyl) propionyloxy } 2,2,6, the 6-tetramethyl piperidine, 1,2,3,4-BTCA and 1,2,2,6,6-pentamethyl--4-piperidine alcohols and β, β, β ', β '-tetramethyl--3,9-[2,4,8,10-, four oxaspiros (5,5) undecane] condenses etc. of ethylene glycol.
In polyester of the present invention, in the scope of not damaging purpose of the present invention, can also contain nucleator, weather resisting agent, lubricant, releasing agent, fire retardant, dyestuff, antistatic agent, whipping agent etc.
The poly (lactic acid) composition that contains sulfoacid compound and organic phosphorus compound of the present invention, by the synergy between sulfoacid compound and the organic phosphorus compound, anti-hydrolytic performance is good so that composition has simultaneously, thermostability is high, the good and metal-free advantage of color and luster.With respect to using volatility monobasic sulfonic acid catalyst, such as methylsulfonic acid, tosic acid, adopt non-volatile or difficult volatility dibasic sulfoacid provided by the invention, polybasic sulfoacid catalyzer to carry out polymerization and can obtain much higher molecular weight.With respect to metal/monobasic sulfonic acid composite catalyst, adopt provided by the invention two, the polybasic sulfoacid catalyzer carries out polymerization that the products therefrom thermostability is significantly improved, color and luster is greatly improved.The present invention has the advantage of aforementioned two kinds of methods concurrently and without corresponding shortcoming, so that the performance of the range of application of poly(lactic acid) and the finished product all is greatly improved.In addition, the importing of organic phosphorus compound has then significantly improved the anti-hydrolytic performance of poly(lactic acid) and composition thereof.Simultaneously provided by the inventionly make catalyzer prepares high molecular weight polyesters at short notice by the direct condensation of lactic acid method with dibasic sulfoacid and/or polybasic sulfoacid, make direct condensation prepare the method for aliphatic polyester in the industrial possibility that becomes.The method can shorten reaction time, has obtained to have simultaneously the polyester of high molecular, high-melting-point and high thermal stability.Prepare polyester by the present invention, its technique simple and stable, polymerization time are short, cost is relatively cheap and the pure not metal ion of product etc.
Embodiment
The invention will be further described below in conjunction with embodiment, but this does not illustrate that the present invention only limits to these embodiment.
For being described as follows of the test that relates among the embodiment:
Weight-average molecular weight (Mw), the Japanese Shimadzu LCsolution GPC of company, 30 ℃, chromatographic grade chloroform leacheate, PS standard.
Fusing point (Tm), the DSC Q-100 of U.S. TA company.Sample is 200 ℃ of meltings after 2 minutes, at the speed borehole cooling to 0 of 20 ℃/min ℃, is warmed up to 200 ℃ again under 0 ℃ of speed with 20 ℃/min.Tm determines that by this heating curve its value is the thermal spike of melting peak.
Hydrolysis, the GL-04KA of Guangzhou Espec Environmental Equipment Co., Ltd type climatic chamber, 60 ℃, processed 5 days under 90% relative humidity, measure the weight-average molecular weight that is hydrolyzed the front and back polyester with GPC, calculated the range of decrease of weight-average molecular weight by the molecular weight of front and back.
Sulphur content is through AQF-100 (Mitsubishi chemistry) combustion method pre-treatment, by IC (ICS-2000, Dionex) quantitative assay.
Phosphorus element content obtains according to add-on, polyester calculation of yield, in the mass percent (ppm) of phosphoric with respect to the poly (lactic acid) composition quality.
Embodiment 1:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,3-the third disulfonic acid 8.61mg (add-on take element sulphur with respect to monomer mass as 15ppm, that is, C S0=15ppm, lower same).Then system temperature rises to 150 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.2KPa and pressure remained under the 0.2KPa condition melt polymerization 4 hours (amounting to 6 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain polyester product.The observed yield Y% that weighing gets whole polymerization process is 72%.This polyester product is added trimethyl phosphite 99 38.9mg after 180 ℃ of lower meltings fully, fully stir after 0.5 hour and pour out, cooling obtains polymer blend.
By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:21.2 ten thousand
Fusing point Tm:168 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 19%
Thermal destruction speed: 0.03wt%/min
Sulphur content C in the product Sp: 20ppm
The residual rate R%:97% of catalyzer
Embodiment 2:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,20-eicosane disulfonic acid 7719.8mg (6210ppm).Then system temperature rises to 160 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization 4 hours (amounting to 6 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain polyester product.The observed yield Y% that weighing gets whole polymerization process is 71%.Get 10g gained polyester product, fully dissolve with the 50ml chloroform, in the gained polyester liquid, add trimethyl phosphite 99 6213.5mg, and behind the Uniform Dispersion solution placed under 60 ℃ of the vacuum drying ovens and remove chloroform, obtain polymer blend.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:16.6 ten thousand
Fusing point Tm:166 ℃
Melt color and luster: slightly black
The molecular weight range of decrease after the hydrolysis: 23%
Thermal destruction speed: 0.05wt%/min
Sulphur content C in the product Sp: 9000ppm
The residual rate R%:100% of sulfonic acid catalyst
Phosphorus element content C in the product Np: 5000ppm
Embodiment 3:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,3-the third disulfonic acid 240.75mg (C S0=420ppm).Then system temperature rises to 160 ℃, with pressure in 2 hours progressively from normal pressure be reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization and (amounts to 6 hours) after 4 hours after cooling obtain the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 155 ℃ of solid state polymerizations 24 hours.After passing into nitrogen and making system recover normal pressure, add behind the 1928.6mg methylpyridine phosphorus that pear shape bottle to be immersed temperature be in 180 ℃ the silicone oil bath 30 minutes in the pear shape bottle, obtain poly (lactic acid) composition after the cooling.The observed yield Y% that weighing gets whole polymerization process is 70%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:18.4 ten thousand
Fusing point Tm:165 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 18%
Thermal destruction speed: 0.01wt%/min
Sulphur content C in the product Sp: 588ppm
The residual rate R%:98% of sulfonic acid catalyst
Embodiment 4:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add methylene-sulfonic acid 24.8mg (C S0=50ppm) and triphenyl phosphorus 232.7mg.Then system temperature rises to 160 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization 12 hours (amounting to 14 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain the poly(lactic acid) product.The observed yield Y% that weighing gets whole polymerization process (comprising melt polymerization and solid state polymerization, lower same) is 69%.
By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:7.6 ten thousand
Fusing point Tm:166 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 30%
Thermal destruction speed: 0.09wt%/min
Sulphur content C in the product Sp: 55ppm
The residual rate R%:75% of sulfonic acid catalyst
Embodiment 5:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ under the nitrogen gas stream of 100L/h, dewatered 2.5 hours.After adding 1,3-the third disulfonic acid 248.7mg (Cs0=433ppm), with system temperature rise to 160 ℃ and under 160 ℃ and nitrogen gas stream melt polymerization 6 hours, pour out, cool off and obtain the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven were taken out after 2 hours and smash.20g prepolycondensate particle (particle diameter 1-3mm) is put into stainless-steel pipe (internal diameter 2cm, long 10cm), pass into the nitrogen gas stream (100L/h) that has heated from the steel pipe bottom.With steel pipe and nitrogen pipeline (long 3m) is put into oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 160 ℃ of solid state polymerizations 20 hours.Take out particle and obtain polyester product.The observed yield Y% that weighing gets whole polymerization process is 70%.With the first pre-mixing 50 minutes in high-speed mixer of the above-mentioned poly(lactic acid) product of 10g and 79.8mg Pyrimithate and 48.5mg triethyl phosphate, then mixture is added twin screw extruder mixing extruding pelletization, extruder temperature is set as: 120 ℃ of feeding sections, 175 ℃ of mixing section temperature, 180 ℃ of fluxing zone temperature, 175 ℃ of head temperatures.By the product sample is tested, obtain following salient features: weight-average molecular weight Mw:16.7 ten thousand
Fusing point Tm:170 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 20%
Thermal destruction speed: 0.02wt%/min
Sulphur content C in the product Sp: 600ppm
The residual rate R%:97% of sulfonic acid catalyst
Embodiment 6:
After adding the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, under nitrogen protection, add 1,3,5-naphthalene trisulfonic acid 159.5mg (Cs0=231ppm).Oil bath temperature is risen to 150 ℃ subsequently, in 60 minutes, system pressure progressively is reduced to 5KPa and polycondensation 2 hours under 5KPa from normal pressure; Then system temperature rises to 180 ℃, and pressure progressively was reduced to 0.2KPa and pressure was remained under the 0.2KPa condition melt polymerization after 14 hours in 2 hours, adds this ester of tricresyl phosphate 4849.1mg, and cooling obtains poly (lactic acid) composition.The observed yield Y% that weighing gets whole polymerization process is 71%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:16.5 ten thousand
Fusing point Tm:161 ℃
Melt color and luster: slightly black
The molecular weight range of decrease after the hydrolysis: 42%
Thermal destruction speed: 0.05wt%/min
Sulphur content Csp:322ppm in the product
The residual rate R%:95% of sulfonic acid catalyst
Embodiment 7:
After adding the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, under nitrogen protection, add Isosorbide-5-Nitrae-Ding disulfonic acid 893mg (C S0=1455ppm).Oil bath temperature is risen to 150 ℃ subsequently, in 60 minutes, system pressure progressively is reduced to 5KPa and polycondensation 2 hours under 5KPa from normal pressure; Then system temperature rises to 180 ℃, pressure progressively was reduced to 0.2KPa and pressure is remained under the 0.2KPa condition melt polymerization pour out after 4 hours in 2 hours, and cooling obtains prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 155 ℃ of solid state polymerizations 20 hours.Take out powder and obtain polyester product.The observed yield Y% that weighing gets whole polymerization process is 72%.Get the above-mentioned poly(lactic acid) product of 80g 175 ℃ of lower meltings, adding triphenylphosphate 1963.3mg and lythidathion 1133.1mg also stirs after 30 minutes and pours out, and cooling obtains poly (lactic acid) composition.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:22.4 ten thousand
Fusing point Tm:170 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 29%
Thermal destruction speed: 0.02wt%/min
Sulphur content Csp:843ppm in the product
The residual rate R%:99% of sulfonic acid catalyst
Embodiment 8:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 5-hydroxyl-1,3,7-dodecane trisulfonic acid 105.5mg (132ppm).Then system temperature rises to 160 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization 4 hours (amounting to 6 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain polyester product.The observed yield Y% that weighing gets whole polymerization process is 71%.Get 10g gained poly(lactic acid) product, fully dissolve with the 50ml chloroform, in gained poly(lactic acid) solution, add 140mg trimethyl phosphite 99 and 326.3mg triphenylphosphate, after dissolving, solution placed under 60 ℃ of the vacuum drying ovens and remove chloroform, obtain poly (lactic acid) composition.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:18.2 ten thousand
Fusing point Tm:170 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 22%
Thermal destruction speed: 0.07wt%/min
Sulphur content C in the product Sp: 1560ppm
The residual rate R%:100% of sulfonic acid catalyst
Embodiment 9:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,3-the third disulfonic acid 181.5mg (C S0=316ppm) and 1-naphthalene phosphoric acid 2198.5mg.Then system temperature rises to 160 ℃, and pressure progressively is being reduced to 50kPa, 2KPa, 0.4KPa, 0.3KPa, 0.2KPa and 0.1KPa from normal pressure.In turn under pressure is the condition of 50kPa, each melt polymerization is poured out after 6 hours (amounting to 36 hours) and is obtained the poly(lactic acid) product under the condition of 2KPa, under the condition of 0.4KPa, under the condition of 0.3KPa, under the condition of 0.2KPa and under the condition of 0.1KPa.The observed yield Y% that weighing gets whole polymerization process is 66%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:12.6 ten thousand
Fusing point Tm:164 ℃
Melt color and luster: little Huang
The molecular weight range of decrease after the hydrolysis: 36%
Thermal destruction speed: 0.05wt%/min
Sulphur content C in the product Sp: 469ppm
The residual rate R%:98% of sulfonic acid catalyst
Embodiment 10:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,10-disulfonic acid in last of the ten Heavenly stems 47.6mg (C S0=56ppm).Then system temperature rises to 160 ℃, pressure progressively was reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization 4 hours (amounting to 6 hours) from normal pressure in 2 hours after, in melt, add 285.8mg phosphorous acid and ethyl ester and 324.7mg methylpyridine phosphorus, pour out after fully stirring, cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 1KPa.Pear shape bottle immersed in the silicone oil bath and oil bath temperature is raised to 90 ℃, 100 ℃, 110 ℃ and keeping at each temperature 1 hour in turn.(corresponding pressure at each temperature is 2KPa, 1KPa, 0.5KPa, 0.3KPa, 0.2KPa, 0.2KPa, 0.1KPa and 0.1KPa in turn) each solid state polymerization 12 hours under 130,140,150,155,160,162,164 and 166 ℃ amounts to solid state polymerization 96 hours subsequently.Take out powder and obtain the poly(lactic acid) product.The observed yield Y% that weighing gets whole polymerization process is 70%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:11.6 ten thousand
Fusing point Tm:167 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 23%
Thermal destruction speed: 0.06wt%/min
Sulphur content C in the product Sp: 2046ppm
The residual rate R%:100% of sulfonic acid catalyst
Embodiment 11:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,3-the third disulfonic acid 181.3mg (C S0=316ppm) and three (2-furyl) phosphine 861.8mg.Then system temperature rises to 160 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization 4 hours (amounting to 6 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain the poly(lactic acid) product.The observed yield Y% that weighing gets whole polymerization process is 72%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:16.9 ten thousand
Fusing point Tm:168 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 38%
Thermal destruction speed: 0.009wt%/min
Sulphur content C in the product Sp: 426ppm
The residual rate R%:97% of sulfonic acid catalyst
Embodiment 12:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 2 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,3-the third disulfonic acid 363.0mg (Cs0=632ppm).Then system temperature rises to 160 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization 4 hours (amounting to 6 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain the poly(lactic acid) product.Get 10g gained poly(lactic acid) product, fully dissolve with the 50ml chloroform, in the gained polyester liquid, add trimethyl phosphite 99 21.4mg, triphenylphosphate 49.9mg and pririmiphos_methyl 46.7mg, after dissolving, solution placed under 60 ℃ of the vacuum drying ovens and remove chloroform, obtain poly (lactic acid) composition.The observed yield Y% that weighing gets whole polymerization process is 70%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:22.5 ten thousand
Fusing point Tm:170 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 31%
Thermal destruction speed: 0.006wt%/min
Sulphur content C in the product Sp: 858ppm
The residual rate R%:95% of sulfonic acid catalyst
Embodiment 13:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 2 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,3-the third disulfonic acid 363.0mg (Cs0=632ppm).Then system temperature rises to 160 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization 4 hours (amounting to 6 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain the poly(lactic acid) product.Get 10g gained poly(lactic acid) product and put into pear shape bottle, add behind lythidathion 404.8mg and the triphenylphosphate 466.1mg that pear shape bottle to be immersed temperature be to take out after 30 minutes in 180 ℃ the silicone oil bath to obtain poly (lactic acid) composition.The observed yield Y% that weighing gets whole polymerization process is 71%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:24.6 ten thousand
Fusing point Tm:171 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 20%
Thermal destruction speed: 0.005wt%/min
Sulphur content C in the product Sp: 855ppm
The residual rate R%:96% of sulfonic acid catalyst
Embodiment 14:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 2 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,3-the third disulfonic acid 538.8mg (Cs0=938ppm).Then system temperature rises to 160 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization 4 hours (amounting to 6 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain the poly(lactic acid) product.Get 10g gained poly(lactic acid) product and put into Glass tubing, add 1,6-(two diphenyl phosphine) hexane 1590.8mg and be that 180 ℃ convection oven is taken out after 30 minutes and obtained poly (lactic acid) composition with putting into temperature after the Glass tubing sealing.The observed yield Y% that weighing gets whole polymerization process is 70%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:20.9 ten thousand
Fusing point Tm:170 ℃
Melt color and luster: water white transparency
The molecular weight range of decrease after the hydrolysis: 30%
Thermal destruction speed: 0.005wt%/min
Sulphur content C in the product Sp: 1300ppm
The residual rate R%:97% of sulfonic acid catalyst
Comparative example 1:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 120 ℃ dewater.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add tosic acid 612.3mg (C S0=632ppm).Then system temperature rises to 160 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.3KPa and pressure remained under the 0.3KPa condition melt polymerization 4 hours (amounting to 6 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain polyester product.The observed yield Y% that weighing gets whole polymerization process is 72%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:15.7 ten thousand
Fusing point Tm:167 ℃
Melt color and luster: colourless, slightly muddy
The molecular weight range of decrease after the hydrolysis: 56%
Thermal destruction speed: 0.7wt%/min
Sulphur content C in the product Sp: 184ppm
The residual rate R%:21% of sulfonic acid catalyst
Comparative example 2:
After injecting the Pfansteihl aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.Install agitator at four-hole boiling flask, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, oil bath temperature is risen to 180 ℃ dewater.System pressure progressively is reduced to 10KPa from normal pressure in the dehydration beginning 60 minutes; Under 10KPa, continue subsequently dehydration 1.5 hours (amounting to dehydration 2.5 hours); At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add 1,3-the third disulfonic acid 363.0mg (C S0=632ppm).Then system temperature rises to 210 ℃, and pressure was progressively poured out after normal pressure is reduced to 0.5KPa and pressure remained under the 0.5KPa condition melt polymerization 2 hours (amounting to 4 hours) in 2 hours, and cooling obtains the poly(lactic acid) prepolymer.Prepolymer 100 degrees centigrade of lower crystallizations in vacuum drying oven are taken out after 2 hours and pulverized.Be that the prepolycondensate powder 100g of 100-250um puts into behind the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times with particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Immerse pear shape bottle in the silicone oil bath and oil bath temperature is raised to 110 ℃ after kept 2 hours.Be warming up to subsequently 158 ℃ of solid state polymerizations 24 hours.Take out powder and obtain polyester product.The observed yield Y% that weighing gets whole polymerization process is 70%.By the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:18.5 ten thousand
Fusing point Tm:169 ℃
Melt color and luster: little Huang
The molecular weight range of decrease after the hydrolysis: 75%
Thermal destruction speed: 0.02wt%/min
Sulphur content C in the product Sp: 850ppm
The residual rate R%:94% of sulfonic acid catalyst
In order to show more intuitively the present invention ground effect, representational embodiment and comparative example are summarized in the table 1.From table 1, can be clear that and adopt the poly (lactic acid) composition of gained of the present invention to have simultaneously the good advantage of high molecular, good color and luster and anti-hydrolytic performance.Poly(lactic acid) for using binary or polybasic sulfoacid catalyzer adopts poly (lactic acid) composition that contains organic compounds containing nitrogen provided by the invention and preparation method thereof, can obtain much higher hydrolytic resistance and the more excellent color and luster that gets.
Table 1
Embodiment Embodiment 1: Embodiment 2: Embodiment 3: Embodiment 4: Embodiment 5: Embodiment 6: Embodiment 15: Comparative example 1: Comparative example 2:
Poly(lactic acid) monomer and quality 90wt%L-lactic acid 200g 90wt%L-lactic acid 200g 90wt%L-lactic acid 200g 90wt%L-lactic acid 200g 90wt%L-lactic acid 200g 90wt%L-lactic acid 200g 90wt%L-lactic acid 200g 90wt%L-lactic acid 200g 90wt%L-lactic acid 200g
Sulfoacid compound and quality 1,3-the third disulfonic acid 1275.7mg 1,20-eicosane disulfonic acid 8701.9mg 1,3-the third disulfonic acid 226.4mg Methylene-sulfonic acid 24.8mg 1,3-the third disulfonic acid 363.0mg 1,3,5-naphthalene trisulfonic acid 436.5mg 1,3-the third disulfonic acid 363.0mg Tosic acid 612.3mg 1,3-the third disulfonic acid 363.0mg
Sulfoacid compound add-on C s0/ppm 2221 7000 395 50 632 632 632 632 632
Melt polymerization conditions 150℃*0.3KP a*6h 160℃*0.3KPa *6h 160℃*0.3K Pa*6h 160℃*0.3K Pa*12h 160℃*6h* N 2Stream 180℃*0.2 KPa*6h 160℃*0.2 KPa*6h 160℃*0.3KP a*6h 210℃*0.5KP a*2h
Solid phase polymerization conditions 158℃*24h 158℃*24h 155℃*24h 158℃*24h 160℃*20h - 158*20h 158℃*24h 158℃*24h
Observed yield Y% 72％ 71％ 70％ 69％ 70％ 71％ 71％ 72％ 70％
Organic compounds containing nitrogen and quality Didecylamine 10825.8mg Ursol D 357.6mg 2-amino-4-methoxyl-6-methylpyrimidine 280.5mg Trilaurylamine (Tridodecylamine 55.6mg Pyrimidine 9.58mg N-Methylimidazole 10.9mg 2-aminopyrimidine 271.5mg Pyrimidine 296.6mg Nothing Nothing
The organic compounds containing nitrogen joining day After solid state polymerization finishes After solid state polymerization finishes After solid state polymerization finishes Before the melt polymerization After solid state polymerization finishes After melt polymerization finishes After solid state polymerization finishes - -
The weight-average molecular weight range of decrease after the hydrolysis 33％ 30％ 18％ 23％ 22％ 41％ 11％ 56％ 75％
Thermal destruction speed wt%/min 0.03 0.05 0.01 0.08 0.02 0.05 0.005 0.11 0.02
Sulphur content Csp in the product a 2995 9851 556 55 876 881 864 184 850
The residual rate R% of sulfonic acid catalyst b 97％ 100％ 98％ 75％ 97％ 99％ 97％ 21％ 94％
Nitrogen element content/ppm 3093 9259 - 12 - - - Nothing Nothing
Nitrogen element and element sulphur mol ratio in the composition 3.00 2.15 - 0.50 - - - - -

Claims (23)

1. a poly (lactic acid) composition that contains sulfoacid compound and organic phosphorus compound is characterized in that containing in this poly (lactic acid) composition poly(lactic acid), sulfoacid compound and organic phosphorus compound; Wherein said sulfoacid compound is selected from one or more in the salt of salt, polybasic sulfoacid, polybasic sulfoacid of dibasic sulfoacid, dibasic sulfoacid, and described organic phosphorus compound is selected from one or more in fatty compounds, aromatics or the heterogeneous ring compound that contains phosphorus atom;
Wherein, the content of described sulfoacid compound in composition is with group-SO 3The quality of-middle sulphur atom is counted 10ppm～10000ppm; The content of described organic phosphorus compound in poly (lactic acid) composition is counted 10ppm～10000ppm with the quality of phosphorus atom; In the organic phosphorus compound in the mole number of phosphorus atom and the sulfoacid compound ratio of the mole number of sulphur atom between 0.5 to 6;
Wherein, described dibasic sulfoacid refers to contain in the molecular formula two sulfonic compounds; Polybasic sulfoacid refers to contain in the molecular formula the sulfonic compound more than three.
2. poly (lactic acid) composition according to claim 1 is characterized in that described sulfoacid compound is the salt of salt, polybasic sulfoacid or the polybasic sulfoacid of nonvolatile dibasic sulfoacid, dibasic sulfoacid.
3. poly (lactic acid) composition according to claim 2 is characterized in that described sulfoacid compound is the salt of salt, polybasic sulfoacid or the polybasic sulfoacid of nonvolatile aliphatic dibasic sulfoacid, dibasic sulfoacid.
4. the described poly (lactic acid) composition of any one according to claim 1～3, it is characterized in that carbonatoms is 1～30 in the molecular formula of dibasic sulfoacid compound in the described sulfoacid compound, carbonatoms is 3～50 in the molecular formula of described polybasic sulfoacid compound.
5. poly (lactic acid) composition according to claim 1 is characterized in that the content of described sulfoacid compound in composition is with group-SO 3The quality of-middle sulphur atom is counted 300ppm～3000ppm.
6. poly (lactic acid) composition according to claim 1 is characterized in that carbonatoms is 1～40 in the described fatty compounds that contains phosphorus atom.
7. poly (lactic acid) composition according to claim 1; it is characterized in that the described fatty compounds that contains phosphorus atom is selected from trimethyl phosphite 99; triethyl phosphate; the tricresyl phosphate propyl ester; tributyl phosphate; the tricresyl phosphate tert-butyl ester; trioctyl phosphate; dimethyl phosphate; diethyl phosphoric acid; dioctylphosphoric acid ester; DCP; trimethyl phosphite; triethyl-phosphite; the tricresyl phosphite isopropyl ester; tributyl phosphate; tricresyl phosphite isodecyl ester; dimethylphosphite; diethyl phosphite; phosphorous acid diisopropyl fat; di-n-butyl phosphite; tri isopropyl phosphorite; tetraisopropyl methylene diphosphate; the triallyl phosphoric acid ester; vinyl phosphate; 3-[three (methylol) phosphorus base] propionic ester; tricresyl phosphate (2; the 3-dibromopropyl) ester; triethyl oxygen six phosphoric acid salt; the triethyl bisphosphate; tricresyl phosphate (butoxyethyl group) ester; the ethylidene pyrodust; trimethylammonium phosphorus; triethyl phosphine; the tripropyl phosphine; tri isopropyl phosphine; tributylphosphine; three tertiary butyl phosphines; tricyclohexyl phosphine; tri-n-octyl phosphine; three normal-butyl phosphine oxides; three cyclopentyl phosphines; trioctylphosphine; 3-phosphonate group propionic acid; trimethyl phosphono acetate; trimethylammonium phosphono formate; phosphono propionic acid triethyl; 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid; the acetonyl diethyl phosphonate; two (diphenylphosphine) methane; 1; the 2-(diphenylphosphine) ethane; 1; the 5-(diphenylphosphine) pentane or 1,6-(diphenylphosphine) in the hexane one or more.
8. poly (lactic acid) composition according to claim 1, it is characterized in that the described aromatics that contains phosphorus atom is selected from triphenyl phosphorus, the triphenylphosphine polymkeric substance, diphenylphosphine, three p-methylphenyl phosphorus, triphenylphosphinc oxide, triphenylphosphate, triphenyl phosphite, tritolyl phosphate, di(2-ethylhexyl)phosphate cresols ester, three (p-nitrophenyl) phosphoric acid ester, 1-naphthalene phosphoric acid, three pairs of toluene phosphoric acid ester, three (2, the 4-di-t-butyl) phenyl-phosphite, three (2, the 6-Dimethoxyphenyl) phosphorus, diphenyl 2 ethylhexyl phosphate, paraoxon, tricresyl phosphate (m-tolyl ester), 2-(di-t-butyl phosphine) biphenyl, three (2-tolyl) phosphine, 1, two (diphenyl phosphine) butane of 4-, two (diphenyl phosphine) propane of 1,3-, three basic Phenylphosphines, 1-triphenylphosphine-2-acetone, the allyl group diphenylphosphine, three (4-methoxyphenyl) phosphorus, diethyl phenyl phosphine, the ethyl diphenylphosphine, isopropyl diphenyl base phosphine, the phenyl dicyclohexylphosphontetrafluoroborate, diphenylcyclohexyl phosphine, in phenylbenzene methoxy base phosphine or the phenylbenzene oxyethyl group phosphine one or more.
9. poly (lactic acid) composition according to claim 1 is characterized in that the described heterogeneous ring compound that contains phosphorus atom is selected from one or more in furan derivatives, thiazole derivative, thiophene derivant, imdazole derivatives, pyridine derivate, pyridazine derivatives, pyrimidine derivatives, pyrazines derivatives or the purine derivative that contains phosphoric.
10. according to claim 1 or 9 described poly (lactic acid) compositions, it is characterized in that the described heterogeneous ring compound that contains phosphorus atom is selected from one or more in adenine phosphate, mephosfolan, isoxathion, methylpyridine phosphorus, Pyrimithate, lythidathion, pririmiphos_methyl, 1-butyl-3-Methylimidazole dibutyl phosphate salt, three (2-furyl) phosphine, three (2-thienyl) phosphine, three (4-morpholino) phosphine or the diphenyl-2-pyridyl phosphine.
11. poly (lactic acid) composition according to claim 1, the weight-average molecular weight that it is characterized in that described poly(lactic acid) is 0.5 ten thousand～300,000.
12. poly (lactic acid) composition according to claim 1, when it is characterized in that described poly (lactic acid) composition is processed 5 days under 60 ℃, the condition of relative humidity 90%, the fall of the weight-average molecular weight of poly(lactic acid) is no more than 50%.
13. poly (lactic acid) composition according to claim 1 is characterized in that described poly (lactic acid) composition temperature is that its thermal weight loss speed is less than 0.1wt%/min under 200 ℃ the condition.
14. the preparation method who contains the poly (lactic acid) composition of sulfoacid compound and organic phosphorus compound claimed in claim 1 is characterized in that may further comprise the steps:
A: under inert gas or pressure be in the decompression situation of 50～0.1KPa, add organic phosphorus compound when adding dibasic sulfoacid or polybasic sulfoacid as catalyzer after, lactic acid monomer or its oligopolymer are carried out melt phase polycondensation 2～30h;
B: the poly(lactic acid) prepolymer that melt phase polycondensation obtains after crystallization treatment, under inert gas or pressure be to carry out 2～100 hours solid state polymerizations in the decompression situation of 0.05～2KPa;
Wherein, described dibasic sulfoacid refers to contain in the molecular formula two sulfonic compounds; Polybasic sulfoacid refers to contain in the molecular formula the sulfonic compound more than three.
15. the preparation method who contains the poly (lactic acid) composition of sulfoacid compound and organic phosphorus compound claimed in claim 1 is characterized in that may further comprise the steps:
A: under inert gas or pressure be in the decompression situation of 50～0.1KPa, add dibasic sulfoacid or polybasic sulfoacid and as catalyzer lactic acid monomer or its oligopolymer carried out melt phase polycondensation 2～30h;
B: add behind the organic phosphorus compound poly(lactic acid) prepolymer crystallization treatment;
C: with prepolymer under the inert gas or pressure be to carry out 2～100 hours solid state polymerizations in the decompression situation of 0.05～2KPa;
Wherein, described dibasic sulfoacid refers to contain in the molecular formula two sulfonic compounds; Polybasic sulfoacid refers to contain in the molecular formula the sulfonic compound more than three.
16. the preparation method who contains the poly (lactic acid) composition of sulfoacid compound and organic phosphorus compound claimed in claim 1 is characterized in that may further comprise the steps:
A: under inert gas or pressure be in the decompression situation of 50～0.1KPa, add dibasic sulfoacid or polybasic sulfoacid and as catalyzer lactic acid monomer or its oligopolymer carried out melt phase polycondensation 2～30h;
B: the poly(lactic acid) prepolymer that melt phase polycondensation obtains after crystallization treatment, under inert gas or pressure be to carry out 2～100 hours solid state polymerizations in the decompression situation of 0.05～2KPa;
C: in the solid state polymerization product, add organic phosphorus compound;
Wherein, described dibasic sulfoacid refers to contain in the molecular formula two sulfonic compounds; Polybasic sulfoacid refers to contain in the molecular formula the sulfonic compound more than three.
17. the preparation method of the described poly (lactic acid) composition of any one according to claim 14～16 is characterized in that described sulfonic acid is nonvolatile dibasic sulfoacid or nonvolatile polybasic sulfoacid.
18. the preparation method of the described poly (lactic acid) composition of any one according to claim 14～16 is characterized in that described sulfonic acid is preferably non-volatile binary aliphatic sulfonic acid or non-volatile aliphatics polybasic sulfoacid.
19. the preparation method of the described poly (lactic acid) composition of any one according to claim 14～16 is characterized in that carbonatoms is 1～30 in the molecular formula of described dibasic sulfoacid, carbonatoms is 3～50 in the molecular formula of described polybasic sulfoacid.
20. the preparation method of the described poly (lactic acid) composition of any one according to claim 14～16 is characterized in that the add-on of described sulfonic acid is with sulfonate radical SO 3The quality of sulphur atom is counted lactic acid quality 10～8000ppm among the H.
21. the preparation method of the described poly (lactic acid) composition of any one according to claim 14～16 is characterized in that the add-on of described sulfonic acid is with sulfonate radical SO 3The quality meter of sulphur atom is preferably lactic acid quality 300～3000ppm among the H.
22. the preparation method of the described poly (lactic acid) composition of any one according to claim 14～16 is characterized in that the residual rate of described sulfoacid compound in final composition is not less than 50% in the quality of sulphur atom; The content of sulfoacid compound in final composition is counted 300-3000ppm with the quality of sulphur atom.
23. the preparation method of the described poly (lactic acid) composition of any one according to claim 14～16 is characterized in that described organic phosphorus compound is selected from one or more in fatty compounds, aromatics or the heterogeneous ring compound that contains phosphorus atom; The add-on of described organic phosphorus compound is counted the 10ppm～10000ppm of lactic acid quality with the quality of phosphoric; In the organic phosphorus compound in the mole number of phosphorus atom and the sulfoacid compound ratio of the mole number of sulphur atom between 0.5 to 6.
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