CN102807670B - A kind of copolymer of poly lactic acid and preparation method thereof - Google Patents
A kind of copolymer of poly lactic acid and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of copolymer of poly lactic acid and preparation method thereof, this multipolymer with lactic acid and comonomer for raw material, in the presence of a catalyst, melt polymerization 5-80 hour at the temperature of the pressure of 0.01-30KPa and 160-230 DEG C.Prepare possess simultaneously higher molecular weight and higher glass transition temperature containing aromatic ring di-carboxylic acid unit, alicyclic ring glycol unit, or the copolymer of poly lactic acid also containing alicyclic ring di-carboxylic acid unit.The method adopts melt polymerization single stage method, and technique is directly simple.And improve the shortcoming of the heat-resisting difference of poly(lactic acid), improve its range of application, the packaging field of higher heat resistant requirements can be widely applied to.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of method of copolymer of poly lactic acid and preparation thereof.
Background technology
Enter 21 century, environmental pollution and shortage of resources become global problem, are also more and more subject to people's attention simultaneously.Be that the synthesized polymer material of raw material is widely used with oil, significant contribution has been made to the development of human civilization.But be difficult to after this kind of materials'use recycle, cause " white pollution " problem serious at present; On the other hand, oil is Nonrenewable resources, the shortage of resources problem that more and more a large amount of consumption makes facing mankind serious.People expect degradative plastics, especially the degradable material of renewable resources origin research and development and application can greatly alleviate this two large problems in the near future.
Much poly(lactic acid) (PLA) is more a kind of degradable material of research application at present, it is the lactic acid obtained with amylofermentation (or chemosynthesis) is a kind of environment-friendly material that basic raw material prepares, it not only has good physicals, also there is good biocompatibility and degradation property, and non-stimulated to human non-toxic.
As hemicrystalline material, poly(lactic acid) can replace general-purpose plastics to apply in a lot.But its second-order transition temperature (Tg), below 60 degrees Celsius, limits poly(lactic acid) and applies widely.Improve the resistance toheat of poly(lactic acid) by improving the crystallization of poly(lactic acid) or improving its second-order transition temperature to realize.The crystallizing power wherein improving poly(lactic acid) mainly comprises the research of the following aspects: the purity 1) improving Pfansteihl; 2) nucleus is added; 3) with inorganic nano material compound; 4) the vertical structure complex compound of poly-L-lactic acid and poly-D lactic acid.The second-order transition temperature improving poly(lactic acid) can carry out the blended or incompatible realization of copolymerization by the stiff polyesters of lactic acid and high glass transition.Because the stiff polyesters consistency of poly(lactic acid) and high glass transition is very poor, so the second-order transition temperature of poly(lactic acid) must be improved by copolymerization.
The poly(lactic acid) pertinent literature patent of high glass transition prepared by current copolymerization is little.Only have patent 200580024916.X to record and prepare the copolymer of poly lactic acid that molecular weight can reach the high glass transition of 5W, but it is by utilizing high reaction activity but simultaneously highly toxic carbonyl chloride is just achieved.
Summary of the invention
The object of this invention is to provide a kind of second-order transition temperature and all higher copolymer of poly lactic acid of molecular weight and preparation method thereof.
Object of the present invention can be reached by following measures:
A kind of copolymer of poly lactic acid:
A kind of copolymer of poly lactic acid, this multipolymer contains alicyclic ring diol copolymer unit and aromatic ring di-carboxylic acid copolymerization units.
Consider the impact on second-order transition temperature, alicyclic ring diol copolymer unit contained in copolymer of poly lactic acid of the present invention is the alicyclic ring glycol monomer unit with molecular formula-O-R '-O-, wherein R ' is alicyclic structure, and namely diol copolymer unit is the glycol monomer unit containing alicyclic structure.For preventing branching to be cross-linked, alicyclic ring diol copolymer unit is preferably the group that can not carry out condensation reaction in its molecular structure containing other, and in addition, the present invention has no particular limits for the molecular structure of alicyclic ring diol copolymer unit.
In above-mentioned alicyclic ring diol copolymer unit-O-R '-O-; wherein R ' can be the alicyclic structure of many rings; also can be the alicyclic structure of monocycle; the alicyclic structure of monocycle and many rings can be the alicyclic structure of the substituent monocycle of band and many rings; also can be the alicyclic structure not with substituting group monocycle and many rings; substituting group described in the present invention is the group that can not carry out condensation reaction, as alkyl, alkoxyl group, ester group, acyl group, aldehyde radical, itrile group, nitro or halogen group.Many rings wherein can be volutions, can be condensed ring, also can be bridged rings; Monocycle wherein can be any ring more than ternary and ternary.Alicyclic ring diol copolymer unit is more preferably with substituting group or is not with substituent ring propylene glycol units, cyclobutanediol units, ring pentanediol unit, cyclohexanediol unit, 1,4:3, the two anhydromannitol unit of 6-, Isosorbide-5-Nitrae: 3,6-two dehydration iditol unit, or one or more in isoscrbierite unit; Wherein most preferably be band substituting group or be not with substituent isoscrbierite unit, Isosorbide-5-Nitrae: one or more in the two anhydromannitol unit of 3,6-or Isosorbide-5-Nitrae: 3,6-two dehydration iditol unit.
Aromatic ring di-carboxylic acid copolymerization units contained in copolymer of poly lactic acid of the present invention for having molecular formula is
dibasic carboxylic acid monomers's unit, wherein R is aromatic ring structure.For preventing branching to be cross-linked, aromatic ring di-carboxylic acid copolymerization units is preferably the group that can not carry out condensation reaction in its molecular structure containing other.In addition, the present invention has no particular limits for the molecular structure of aromatic ring di-carboxylic acid copolymerization units.
Above-mentioned aromatic ring di-carboxylic acid copolymerization units
in, R can be the aromatic ring structure of monocycle, also can be the aromatic ring structure of many rings, and the aromatic ring structure of monocycle and many rings can be the aromatic ring structure of the substituent monocycle of band and many rings, also can be the aromatic ring structure not with substituting group monocycle and many rings, above-mentioned record be shown in substituent description.Wherein, in the aromatic ring structure of many rings, two carboxylic carbonyls both can be connected on same aromatic ring, also can be connected on different aromatic rings.Wherein, the aromatic ring structure of monocycle can be any ring more than ternary and ternary.Aromatic ring di-carboxylic acid copolymerization units is more preferably with substituting group or not with one or more in substituent isophthalic acid units, terephthalic acid units or naphthalic acid unit.
The weight-average molecular weight of copolymer of poly lactic acid of the present invention is preferably 50,000-250, and 000, more preferably 100,000-250,000.
The second-order transition temperature of copolymer of poly lactic acid of the present invention is preferably 65 DEG C-120 DEG C, more preferably 75 DEG C-120 DEG C.
Also containing alicyclic ring di-carboxylic acid copolymerization units in copolymer of poly lactic acid of the present invention, contained alicyclic ring di-carboxylic acid copolymerization units for having molecular formula is
dibasic carboxylic acid monomers's unit, " be alicyclic structure, namely alicyclic ring di-carboxylic acid copolymerization units is the dibasic carboxylic acid monomers's unit containing alicyclic structure to wherein R.For preventing branching to be cross-linked, alicyclic ring di-carboxylic acid copolymerization units is preferably the group that can not carry out condensation reaction in its molecular structure containing other.In addition, the present invention has no particular limits for the molecular structure of alicyclic ring di-carboxylic acid copolymerization units.
Above-mentioned alicyclic ring di-carboxylic acid copolymerization units
in, " can be the alicyclic structure of monocycle, also can be the alicyclic structure of many rings to R, and the alicyclic structure of monocycle and many rings can be the alicyclic structure of the substituent monocycle of band and many rings; also can be the alicyclic structure not with substituting group monocycle and many rings, above-mentioned record be shown in substituent description.Wherein, the alicyclic structure of many rings can be volution, can be condensed ring, also can be bridged ring, and two carboxylic carbonyls both can be connected on same alicyclic ring, also can be connected on different alicyclic rings; Wherein, the alicyclic structure of monocycle can be any ring more than ternary and ternary.Alicyclic ring di-carboxylic acid copolymerization units is more preferably with substituting group or is not with substituent ring third dioctyl phthalate unit, ring fourth dioctyl phthalate unit, ring penta dioctyl phthalate unit, cyclohexyl dicarboxylic acid unit, or one or more in ring dioctyl phthalate in heptan unit; Wherein most preferably be band substituting group or be not with substituent cyclohexyl dicarboxylic acid unit.
The preparation method of above-mentioned copolymer of poly lactic acid:
The method prepared of copolymer of poly lactic acid of the present invention with lactic acid and comonomer for raw material, in the presence of a catalyst, melt polymerization 5-80 hour at the temperature of the pressure of 0.01-30KPa and 160-230 DEG C.
Wherein, comonomer comprises alicyclic ring glycol monomer and aromatic ring dibasic carboxylic acid monomers.
Consider the impact on second-order transition temperature, alicyclic ring glycol monomer in copolymer of poly lactic acid preparation method of the present invention is the alicyclic ring glycol monomer with molecular formula HO-R '-OH, wherein R ' is alicyclic structure, and namely alicyclic ring glycol monomer is the glycol monomer containing alicyclic structure.For preventing branching to be cross-linked, alicyclic ring glycol monomer is preferably the group that can not carry out condensation reaction in its molecular structure containing other, and in addition, the present invention has no particular limits for the molecular structure of alicyclic ring glycol monomer.
In above-mentioned alicyclic ring glycol monomer HO-R '-OH, wherein R ' can be the alicyclic structure of many rings, also can be the alicyclic structure of monocycle, the alicyclic structure of monocycle and many rings can be the alicyclic structure of the substituent monocycle of band and many rings, also can be the alicyclic structure not with substituting group monocycle and many rings, substituent description sees above record.Monocycle wherein can be any ring more than ternary and ternary.Alicyclic ring glycol monomer is more preferably with substituting group or is not with substituent ring propanediol monomer, cyclobutanediol monomer, ring pentanediol monomer, cyclohexanediol monomer, 1,4:3, the two anhydromannitol monomer of 6-, Isosorbide-5-Nitrae: 3,6-two dehydration iditol monomer, or one or more in isosorbide monomer; Wherein most preferably be band substituting group or be not with substituent isosorbide monomer, Isosorbide-5-Nitrae: one or more in the two anhydromannitol monomer of 3,6-or Isosorbide-5-Nitrae: 3,6-two dehydration iditol monomer.
Aromatic ring dibasic carboxylic acid monomers in copolymer of poly lactic acid preparation method of the present invention for having molecular formula is
aromatic ring dibasic carboxylic acid monomers, wherein R is aromatic ring structure.For preventing branching to be cross-linked, aromatic ring dibasic carboxylic acid monomers is preferably the group that can not carry out condensation reaction in its molecular structure containing other.In addition, the present invention has no particular limits for the molecular structure of aromatic ring dibasic carboxylic acid monomers.
Above-mentioned aromatic ring dibasic carboxylic acid monomers
in, R can be the aromatic ring structure of monocycle, also can be the aromatic ring structure of many rings, and the aromatic ring structure of monocycle and many rings can be the aromatic ring structure of the substituent monocycle of band and many rings, also can be the aromatic ring structure not with substituting group monocycle and many rings, substituent description sees above record.Wherein, aromatic ring structure two carboxylic carbonyls of many rings both can be connected on same aromatic ring, also can be connected on different aromatic rings; Wherein, the aromatic ring structure of monocycle can be any ring more than ternary and ternary.Aromatic ring structure dibasic carboxylic acid monomers is more preferably with substituting group or not with one or more in substituent m-phthalic acid monomer, terephthalic acid monomers or naphthalene dicarboxylic acid monomers.
In copolymer of poly lactic acid preparation method of the present invention, comonomer also comprises alicyclic ring dibasic carboxylic acid monomers, and described alicyclic ring dibasic carboxylic acid monomers for having molecular formula is
dibasic carboxylic acid monomers, " be alicyclic structure, namely alicyclic ring dibasic carboxylic acid monomers is the dibasic carboxylic acid monomers containing alicyclic structure to wherein R.For preventing branching to be cross-linked, alicyclic ring dibasic carboxylic acid monomers is preferably the group that can not carry out condensation reaction in its molecular structure containing other.In addition, the present invention has no particular limits for the molecular structure of alicyclic ring dibasic carboxylic acid monomers.
Above-mentioned alicyclic ring dibasic carboxylic acid monomers
in, " can be the alicyclic structure of monocycle, also can be the alicyclic structure of many rings to R, and the alicyclic structure of monocycle and many rings can be the alicyclic structure of the substituent monocycle of band and many rings; also can be the alicyclic structure not with substituting group monocycle and many rings, above-mentioned record be shown in substituent description.Wherein, the alicyclic structure of many rings can be volution, can be condensed ring, also can be bridged ring, and two carboxylic carbonyls both can be connected on same alicyclic ring, also can be connected on different alicyclic rings; Wherein, the alicyclic structure of monocycle can be any ring more than ternary and ternary.Alicyclic ring dibasic carboxylic acid monomers is more preferably with substituting group or is not with substituent ring third dioctyl phthalate monomer, ring fourth dioctyl phthalate monomer, ring penta dioctyl phthalate monomer, cyclohexyl dicarboxylic acid monomer, or one or more in ring dioctyl phthalate in heptan monomer; Wherein most preferably be band substituting group or be not with substituent cyclohexyl dicarboxylic acid monomer.
In method of the present invention, joining day section for raw material and catalyzer is not particularly limited, but considers that lactic acid is generally moisture lactic acid aqueous solution, is preferably: lactic acid is under the temperature range of 100 DEG C to 180 DEG C, pressure is reduced to 5KPa from 30KPa gradually, dehydration 0.5-2h; Then add catalyzer and comonomer, reaction pressure is preferably reduced to below 0.01KPa gradually from 30KPa, and temperature of reaction is preferably elevated to more than 210 DEG C gradually from 160 DEG C, under mechanical stirring melt polymerization 5-80h.
Catalyzer described in the preparation method of copolymer of poly lactic acid of the present invention be selected from metal compound as catalyst or acid compounds catalyzer one or more.
Metallic element in above-mentioned metal compound as catalyst be selected from IA-IVA race, IB-VIIB race, group VIII metal element or thulium one or more; Consider catalytic activity, be preferably one or more in Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Sm, Eu, Er, Yb, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Cu, Zn, Cd, Al, Ge, Sn, Pb, Sb, Bi; One or more more preferably in Ti, Mn, Fe, Cu, Zn, Al, Ge, Sn, Pb, Sb or Ce, most preferably are Sn, one or more in Ti, Sb, Zn or Al.Therefore metal compound as catalyst most preferably be tin compound, titanium compound, antimony compounds, one or more in zn cpds or aluminum compound.Above-mentioned metallic compound can be metallic monomer, organometallics or metal inorganic compound.Specifically, metallic compound can be the monomer of above-mentioned metal, halogenide, oxide compound, oxyhydroxide, carbonate, vitriol, nitrate, phosphoric acid salt, silicate, borate, oxymuriate, chromic salt, manganate, arsenate, cyanate, alkyl carboxylate, alkyl dicarboxylic aid's salt, alkyl multi-carboxylate, substituted alkyl carboxylate salt, substituted alkyl dicarboxylate, substituted alkyl multi-carboxylate, aromatic carboxylates, aromatic base dicarboxylate, aromatic base multi-carboxylate, substituted aromatic base carboxylate salt, substituted aromatic base dicarboxylate, substituted aroma hydroxypolycarboxylates, alkylsulfonate, substituted alkyl sulfonate, aromatic sulfonate, substituted aromatic base sulfonate, acetylacetonate, alkyl alkoxide, or substituted alkyl alkoxide etc., metallic compound be preferably the monomer of above-mentioned metal, halogenide, oxide compound, vitriol, borate, alkyl carboxylate, substituted alkyl carboxylate salt, alkyl dicarboxylic aid's salt, substituted alkyl dicarboxylate, alkyl multi-carboxylate, substituted alkyl multi-carboxylate, alkylsulfonate, substituted alkyl sulfonate, aromatic sulfonate, substituted aromatic base sulfonate, acetylacetonate, alkyl alkoxide or substituted alkyl alkoxide, the monomer of the more preferably above-mentioned metal of metallic compound, muriate, oxide compound, vitriol, fluoroborate, acetate, oxalate, octylate, Citrate trianion, metilsulfate, ethyl sulfonate, propyl sulfonic acid salt, butyl sulfosalt, amyl group sulfonate, acetylacetonate or alkyl alkoxide.
To count with metallic element quality as total add-on of the metallic compound of catalyzer in the preparation method of copolymer of poly lactic acid of the present invention and (do not comprise 0 with 0-200000ppm, relative to the quality of lactic acid monomer thing, lower same) as well, be 0-100000ppm preferably, more preferably 10-80000ppm, is preferably 10-40000ppm.Content is too small, may affect catalytic performance; Too high, the mechanical property of copolymer of poly lactic acid may be affected.
Above-mentioned acid compounds catalyzer is one or more in mineral acid or organic acid, specifically can for but be not limited only in sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, boric acid, fluoroboric acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, phospho-wolframic acid, phospho-molybdic acid or sulfonic acid one or more; More preferably sulfuric acid, one or more in phosphoric acid or sulfonic acid.Wherein sulfonic acid can be one or more unitary sulfonic acid, also can be one or more polybasic sulfoacid, can also be their mixture, above-mentioned sulfonic acid can be one or more aliphatic sulfonic simultaneously, and also can be one or more aromatic sulphonic acid, can also be their mixture, specifically, the large compounds of described sulfonic acid for having general formula A-(SO3H) x, wherein x >=1 and be integer, in general x≤30, preferred x≤10, most preferably x≤5, A is hydrocarbon chain, replacement hydrocarbon chain, the aromatic ring of C1-C30 or replaces aromatic ring, sulfonic acid is preferably methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, penta sulfonic acid, own sulfonic acid, heptan sulfonic acid, pungent sulfonic acid, the ninth of the ten Heavenly Stems sulfonic acid, the last of the ten Heavenly stems sulfonic acid, undecane sulfonic acid, dodecane sulfonic acid or eicosane sulfonic acid, methylene-sulfonic acid, ethionic acid, third disulfonic acid, fourth disulfonic acid, penta disulfonic acid, own disulfonic acid, heptan disulfonic acid, pungent 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, 1, 12-dodecane disulfonic acid or 1, 20-eicosane disulfonic acid, Phenylsulfonic acid, substituted benzenesulfonic acid, benzene disulfonic acid, substituted benzene disulfonic acid, naphthene sulfonic acid, replace naphthene sulfonic acid, naphthalene disulfonic acid, replace naphthalene disulfonic acid, Witco 1298 Soft Acid, or 1, 2, 3-third trisulfonic acid etc., the more preferably methylsulfonic acid of sulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, methylene-sulfonic acid, ethionic acid, the third disulfonic acid, fourth disulfonic acid, tosic acid, or 1,5-naphthalene disulfonic acid.
(0 is not comprised by the quality of H+ ion in acid with 0ppm-1000ppm as total add-on of the acid compounds of catalyzer in the preparation method of poly (lactic acid) composition of the present invention, relative to the quality of lactic acid monomer thing, lower same) as well, be better 0.1-400ppm, be preferably 1ppm-250ppm again, more preferably 5ppm-200ppm, that best is 10-100ppm.Too high, the degraded in mechanical properties of product may be caused, too low, while affecting catalytic performance, also may affect the thermostability of product.
In the preparation method of copolymer of poly lactic acid of the present invention, the mol ratio of lactic acid and comonomer total amount is 99/1 ~ 1/99, considers, the principal status of public economy of lactic acid, the optimization of molecular weight and second-order transition temperature, the mol ratio of lactic acid and comonomer total amount is preferably 70/30 ~ 90/10.Generally, for reaching higher molecular weight, the hydroxyl carboxylic ratio making whole system is 1: 1, and in comonomer, the total amount of di-carboxylic acid and the total amount of dibasic alcohol are 1: 1 by equimolar amount ratio.But consider that part dibasic alcohol, under high-temperature vacuum, the feature that transesterify removes volatilization easily occurs, the molar weight ratio of the total amount of comonomer di-carboxylic acid and the total amount of dibasic alcohol can regulate between 1: 1 ~ 1: 1.5, is preferably and regulates between 1: 1 ~ 1: 1.2.
Copolymer of poly lactic acid prepared by the present invention is while acquisition higher molecular weight, second-order transition temperature is greatly improved, thus while keeping its mechanical strength, improve the shortcoming of the heat-resisting difference of poly(lactic acid), improve its range of application, particularly packaging field, transport under preventing hot conditions, storage, and the microwave heating of food product pack, and the softening transform that packaging occurs.The method adopts melt polymerization single stage method, and technique is directly simple.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but this does not illustrate that the present invention is only limitted to these embodiments.
The explanation in the source of various material.
Lactic acid: Musashi is wild;
Comonomer, catalyzer: alpha (Alfa Aesar)
For being described as follows of the test that the present invention relates to:
Weight-average molecular weight (Mw), Japanese Shimadzu Corporation LCsolution GPC, 30 DEG C, chromatographic grade trichloromethane leacheate, PS standard.
Second-order transition temperature (Tg), TA company of U.S. DSC Q-100.Sample 200 DEG C of meltings after 2 minutes, at the speed borehole cooling to 0 DEG C of 20 DEG C/min, then from 0 DEG C to be warmed up to 200 DEG C the speed of 20 DEG C/min.Tg is determined by this heating curve.
Embodiment 1:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 14.6g is added under nitrogen protection, m-phthalic acid 16.6g, stannous acetate 65mg.Then system temperature rises to 210 DEG C, pressure is progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 24 hours pressure being remained on 0.2KPa condition, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:8.3 ten thousand.
Glass transition temperature Tg: 78 DEG C.
Embodiment 2:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 1.46g is added under nitrogen protection, m-phthalic acid 1.66g, sulfuric acid 100ul.Then system temperature rises to 220 DEG C, pressure is progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 4 hours pressure being remained on 0.2KPa condition, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:5.2 ten thousand.
Glass transition temperature Tg: 68 DEG C.
Embodiment 3:
Inject the Pfansteihl aqueous solution 10g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 146g is added under nitrogen protection, m-phthalic acid 166g, sulfuric acid 60ul.Then system temperature rises to 230 DEG C, pressure is progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 20 hours pressure being remained on 0.2KPa condition, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:7.6 ten thousand.
Glass transition temperature Tg: 119 DEG C.
Embodiment 4:
Inject the Pfansteihl aqueous solution 10g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 146g is added under nitrogen protection, m-phthalic acid 166g, ethyl sulfonic acid 1000ul, isopropyl titanate 300ug.Then system temperature rises to 230 DEG C, pressure is progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 10 hours pressure being remained on 0.2KPa condition, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:5.6 ten thousand.
Glass transition temperature Tg: 112 DEG C.
Embodiment 5:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 14.6g is added under nitrogen protection, terephthalic acid 16.6g, sulfuric acid 60ul.Then system temperature rises to 210 DEG C, pressure is progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 44 hours pressure being remained on 0.2KPa condition, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:12.5 ten thousand.
Glass transition temperature Tg: 76 DEG C.
Embodiment 6:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 29.2g is added under nitrogen protection, naphthalic acid 43.2g, antimonous oxide 175mg.Then system temperature rises to 180 DEG C, pressure was progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 4 hours pressure being remained on 0.2KPa condition, system temperature rises to 210 DEG C, and pressure to remain under 0.1Kpa condition repolymerization 24 hours, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:10.5 ten thousand.
Glass transition temperature Tg: 83 DEG C.
Embodiment 7:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, add Isosorbide-5-Nitrae under nitrogen protection: 3,6-two anhydromannitol 29.2g, m-phthalic acid 33.2g, metatitanic acid isopropyl ester 70ul.Then system temperature rises to 180 DEG C, pressure was progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 4 hours pressure being remained on 0.2KPa condition, system temperature rises to 210 DEG C, and pressure to remain under 0.1Kpa condition repolymerization 24 hours, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:9.5 ten thousand.
Glass transition temperature Tg: 80.5 DEG C.
Embodiment 8:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, add Isosorbide-5-Nitrae under nitrogen protection: 3,6-two dehydration iditol 29.2g, m-phthalic acid 33.2g, tetrabutyl titanate 30mg, tosic acid 160ul.Then system temperature rises to 180 DEG C, pressure is progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 44 hours pressure being remained on 0.1KPa condition, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:8.2 ten thousand.
Glass transition temperature Tg: 84 DEG C.
Embodiment 9:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 29.2g is added under nitrogen protection, m-phthalic acid 33.2g, zinc chloride 165mg.Then system temperature rises to 210 DEG C, pressure was progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 4 hours pressure being remained on 0.2KPa condition, system temperature rises to 230 DEG C, and pressure to remain under 0.1Kpa condition repolymerization 72 hours, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:15.6 ten thousand.
Glass transition temperature Tg: 96 DEG C.
Embodiment 10:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, add Isosorbide 29.2g under nitrogen protection, m-phthalic acid 34.4g, metatitanic acid isopropyl ester 140ul.Then system temperature rises to 210 DEG C, pressure is progressively reduced to 0.1KPa from normal pressure in 2 hours and melt polymerization 78 hours pressure being remained on 0.1KPa condition, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:24.6 ten thousand.
Glass transition temperature Tg: 116 DEG C.
Embodiment 11:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, add cyclohexanediol 23.2g under nitrogen protection, m-phthalic acid 33.2g, metatitanic acid isopropyl ester 140ul.Then system temperature rises to 210 DEG C, pressure is progressively reduced to 0.1KPa from normal pressure in 2 hours and melt polymerization 78 hours pressure being remained on 0.1KPa condition, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:8.1 ten thousand.
Glass transition temperature Tg: 76 DEG C.
Embodiment 12:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 29.2g is added under nitrogen protection, m-phthalic acid 8.3g, terephthalic acid 8.3g, isopropyl titanate 140ul.Then system temperature rises to 210 DEG C, pressure was progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 8 hours pressure being remained on 0.2KPa condition, with nitrogen, system pressure is returned to normal pressure again, add cyclohexyl dicarboxylic acid 17.2g, then system temperature rises to 210 DEG C, pressure to remain under 0.1Kpa condition repolymerization 44 hours, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:14.6 ten thousand.
Glass transition temperature Tg: 95 DEG C.
Embodiment 13:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 29.2g is added under nitrogen protection, m-phthalic acid 8.3g, terephthalic acid 8.3g, stannous acetate 65mg, methylsulfonic acid 50ul.Then system temperature rises to 200 DEG C, pressure was progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 8 hours pressure being remained on 0.2KPa condition, with nitrogen, system pressure is returned to normal pressure again, add cyclohexyl dicarboxylic acid 17.2g, then system temperature rises to 210 DEG C, pressure to remain under 0.1Kpa condition repolymerization 46 hours, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:12.7 ten thousand.
Glass transition temperature Tg: 93 DEG C.
Embodiment 14:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 58.4g is added under nitrogen protection, m-phthalic acid 16.6g, terephthalic acid 16.6g, isopropyl titanate 210ul.Then system temperature rises to 200 DEG C, pressure was progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 8 hours pressure being remained on 0.2KPa condition, with nitrogen, system pressure is returned to normal pressure again, add cyclohexyl dicarboxylic acid 34.4g, then system temperature rises to 220 DEG C, pressure to remain under 0.1Kpa condition repolymerization 46 hours, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:10.6 ten thousand.
Glass transition temperature Tg: 108 DEG C.
Embodiment 15:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, Isosorbide 58.4g is added under nitrogen protection, m-phthalic acid 16.6g, terephthalic acid 16.6g, isopropyl titanate 210ul.Then system temperature rises to 200 DEG C, pressure was progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 8 hours pressure being remained on 0.2KPa condition, with nitrogen, system pressure is returned to normal pressure again, add ring fourth dioctyl phthalate 28.8g, then system temperature rises to 220 DEG C, pressure to remain under 0.1Kpa condition repolymerization 46 hours, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:7.9 ten thousand.
Glass transition temperature Tg: 86 DEG C.
Comparative example 1
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, catalyst sulfuric acid 60ul is added under nitrogen protection.Then system temperature rises to 180 DEG C, pressure is progressively reduced to 0.1KPa from normal pressure in 2 hours and melt polymerization 24 hours pressure being remained on 0.1KPa condition, cools to obtain product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:4.8 ten thousand.
Glass transition temperature Tg: 58 DEG C.
Comparative example 2
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, add stannous acetate 51mg and tosic acid 206mg under nitrogen protection.Then system temperature rises to 160 DEG C, pressure was progressively reduced to 0.3KPa from normal pressure in 2 hours and melt polymerization was poured out after 4 hours (amounting to 6 hours) pressure being remained on 0.3KPa condition, cooling obtains PLA prepolymer, then cooling crush, be that the blend powders 100g of 100-250um to put into after the 1L pear shape bottle of Rotary Evaporators with nitrogen replacement 2 times by particle diameter, in 60 minutes, pressure dropped to 0.2KPa.Pear shape bottle to be immersed in silicone oil bath and to keep 2 hours after oil bath temperature is raised to 110 DEG C.Be warming up to 160 DEG C of solid state polymerizations 24 hours subsequently.Take out powder and obtain PLA product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:20.5 ten thousand.
Glass transition temperature Tg: 60.3 DEG C.
Comparative example 3:
Inject the Pfansteihl aqueous solution 100g of 90wt% in 250mL there-necked flask after, flask is put into oil bath.There-necked flask installs agitator, inserts thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and with after nitrogen replacement 3 times, oil bath temperature risen to 120 DEG C and dewater.From dehydration, in 60 minutes, system pressure is progressively reduced to 5KPa from normal pressure; Dehydration 1.5 hours (amounting to dehydration 2.5 hours) is continued subsequently under 5KPa; Now, after system pressure being returned to normal pressure with nitrogen, hexylene glycol 11.8g is added under nitrogen protection, cyclohexyl dicarboxylic acid 17.2g, stannous acetate 65mg, methylsulfonic acid 50ul.Then system temperature rises to 200 DEG C, pressure is progressively reduced to 0.2KPa from normal pressure in 2 hours and melt polymerization 54 hours pressure being remained on 0.2KPa condition, cools to obtain copolymerization product.By testing Product samples, obtain following salient features:
Weight-average molecular weight Mw:11.8 ten thousand.
Glass transition temperature Tg: 59 DEG C.
Claims (8)
1. a copolymer of poly lactic acid, is characterized in that: described lactic acid copolymer contains alicyclic ring diol copolymer unit and aromatic ring di-carboxylic acid copolymerization units; The mol ratio of lactic acid units and copolymerization units total amount is 70/30 ~ 90/10; Described alicyclic ring diol copolymer unit is selected from isoscrbierite unit, Isosorbide-5-Nitrae: one or more in the two anhydromannitol unit of 3,6-or Isosorbide-5-Nitrae: 3,6-two dehydration iditol unit; Described aromatic ring di-carboxylic acid copolymerization units be selected from isophthalic acid units, terephthalic acid units or naphthalic acid unit one or more.
2. copolymer of poly lactic acid according to claim 1, is characterized in that: the weight-average molecular weight of described copolymer of poly lactic acid is 50,000-250,000; Second-order transition temperature is 65 DEG C-120 DEG C.
3. copolymer of poly lactic acid according to claim 1, is characterized in that: also containing alicyclic ring di-carboxylic acid copolymerization units.
4. copolymer of poly lactic acid according to claim 3, is characterized in that: described alicyclic ring di-carboxylic acid copolymerization units is cyclohexyl dicarboxylic acid unit.
5. a preparation method for copolymer of poly lactic acid described in claim 1, is characterized in that: with lactic acid and comonomer for raw material, in the presence of a catalyst, melt polymerization 5-80 hour at the temperature of the pressure of 0.01-30KPa and 160-230 DEG C; Wherein comonomer comprises alicyclic ring glycol monomer and aromatic ring dibasic carboxylic acid monomers; Wherein, the mol ratio of lactic acid and comonomer total amount is 70/30 ~ 90/10; Described alicyclic ring glycol monomer is selected from isosorbide monomer, Isosorbide-5-Nitrae: one or more in the two anhydromannitol monomer of 3,6-or Isosorbide-5-Nitrae: 3,6-two dehydration iditol monomer; Described aromatic ring di-carboxylic acid be selected from m-phthalic acid monomer, terephthalic acid monomers or naphthalene dicarboxylic acid monomers one or more.
6. the preparation method of copolymer of poly lactic acid according to claim 5, is characterized in that: also comprise alicyclic ring dibasic carboxylic acid monomers in described comonomer.
7. the preparation method of copolymer of poly lactic acid according to claim 6, is characterized in that: described alicyclic ring dibasic carboxylic acid monomers is cyclohexyl dicarboxylic acid monomer.
8. the preparation method of copolymer of poly lactic acid according to claim 5, is characterized in that: described catalyzer is one or more in metal compound as catalyst or acid compounds catalyzer; Wherein, metal compound as catalyst is selected from one or more in tin compound, titanium compound, antimony compounds, zn cpds or aluminum compound; Acid compounds catalyzer is selected from one or more in sulfuric acid, phosphoric acid or sulfonic acid.
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| CN1980975A (en) * | 2004-07-09 | 2007-06-13 | 纳幕尔杜邦公司 | Sulfonated aromatic copolyesters containing hydroxyalkanoic acid groups and shaped articles produced therefrom |
| CN101815741A (en) * | 2007-08-09 | 2010-08-25 | 自然工作有限责任公司 | Method for making copolymers of lactide and a 1:4-3:6 dianhydrohexitol |
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| JP2003206337A (en) * | 1994-08-31 | 2003-07-22 | Mitsubishi Chemicals Corp | Manufacturing method of aliphatic polymer copolymer |
| CN1646596A (en) * | 2002-04-22 | 2005-07-27 | 诺瓦蒙特股份公司 | Biodegradable thermoplastic polyesters |
| CN1980975A (en) * | 2004-07-09 | 2007-06-13 | 纳幕尔杜邦公司 | Sulfonated aromatic copolyesters containing hydroxyalkanoic acid groups and shaped articles produced therefrom |
| CN101815741A (en) * | 2007-08-09 | 2010-08-25 | 自然工作有限责任公司 | Method for making copolymers of lactide and a 1:4-3:6 dianhydrohexitol |
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