CN102485768A - Polycarbonate unit-containing polylactic acid copolymer and preparation method thereof - Google Patents
Polycarbonate unit-containing polylactic acid copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN102485768A CN102485768A CN2010105843373A CN201010584337A CN102485768A CN 102485768 A CN102485768 A CN 102485768A CN 2010105843373 A CN2010105843373 A CN 2010105843373A CN 201010584337 A CN201010584337 A CN 201010584337A CN 102485768 A CN102485768 A CN 102485768A
- Authority
- CN
- China
- Prior art keywords
- acid
- lactic acid
- copolymer
- preparation
- prepolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a polycarbonate unit-containing polylactic acid copolymer and a preparation method thereof. The preparation method is characterized in that one or more polycarbonate prepolymers, a function group conditioning agent and lactic acid or a lactic acid prepolymer undergo a polycondensation reaction in the presence of sulfuric acid, sulfonic acid or a sulfonic acid-metal compound composite catalyst system as a catalyst to produce the polycarbonate unit-containing polylactic acid copolymer. The polycarbonate unit-containing polylactic acid copolymer obtained by the preparation method comprises a polycarbonate unit, a dicarboxylic acid unit and a polylactic acid unit, utilizes organisms as monomers, can be prepared easily, has a low production cost, high molecular weight and high Tg, and can be utilized for the fields such as blister package materials, disposable food boxes and the like having high heat-resistant requirements.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to method and this copolymer of poly lactic acid that a kind of preparation contains the unitary poly (lactic acid) composition of aliphatic polycarbonate.
Background technology
POLYACTIC ACID (PLA) is a kind of degradable material of the more relatively renewable resources origin of present Application Research; It is to be a kind of non-stimulated to the human non-toxic environment-friendly material that basic raw material prepares with the lactic acid that amylofermentation (or chemosynthesis) obtains; It not only has good physicals, also has excellent biological compatibility and degradation property.The factor of restriction POLYACTIC ACID widespread use mainly contains two at present: a factor is the production cost height, costs an arm and a leg.Causing the high major cause of production cost is that the polymerization route that present most applicability POLYACTIC ACID adopts is indirect (open loop) method, promptly at first dehydrating condensation between lactic acid molecules is processed lactic acid oligomer, generates the cyclic rac-Lactide by the oligopolymer degraded again; Then the rac-Lactide ring-opening polymerization is generated superpolymer.The preparation of this method and the polylactic acid molecule amount higher, better heat stability, second-order transition temperature and fusing point are all than higher.But (open loop) method production technique is tediously long indirectly, and complex process particularly needs repeatedly to purify and recrystallization in lactide refined, consumes a large amount of reagent, and high production cost has seriously hindered the widespread use of POLYACTIC ACID as a kind of general-purpose plastics material.The factor of another restriction POLYACTIC ACID widespread use is; Compare with general-purpose plastics; The resistance toheat of POLYACTIC ACID is relatively poor; For requiring certain stable on heating material (for example being used for the Blister Package material of drug packaging, the container that is used to hold Foods or drinks, CD, computer or phone housing etc.), the big limitations of its lower second-order transition temperature (Tg=55～62 ℃) its application.Therefore, improve the Tg of polylactic resin, make it can satisfy the active demand that is applied to aspect above-mentioned for current POLYACTIC ACID applied research.
It is one of effective ways that improve POLYACTIC ACID Tg that other monomers or polymkeric substance and the POLYACTIC ACID that employing has a higher Tg forms multipolymer.Can adopt rac-Lactide and other cyclic esters or cyclic carbonate copolymerization to form random or segmented copolymer on the method.USP NO.5006772 discloses a kind of POLYACTIC ACID-poly (propylene carbonate) random copolymers, described simultaneously the employing rac-Lactide and as 1, the method for 3-dioxane-above-mentioned random copolymers of 2-ketone copolymerization.A kind of POLYACTIC ACID-aliphatics cyclic carbonate ester copolymer is disclosed among another piece USP NO.6093792; Employing rac-Lactide and for example 1 have been described simultaneously; 2-O-isopropylidene-D-furyl xylose-3, the method for the above-mentioned multipolymer of 5-cyclic carbonate ester (IPXTC) copolymerization.But the shortcoming of above-mentioned technology is, the comonomer except that rac-Lactide is usually based on non-renewable raw material, and costs an arm and a leg; It is that raw material carries out the method that copolymerization comprises the polyester-carbonate copolymer of Isosorbide repeating unit and rac-Lactide repeating unit with Isosorbide, rac-Lactide and three kinds of monomers of carbonate precursor that Chinese patent CN200880102539 discloses a kind of.Different with foregoing two pieces of USPs, the isosorbide monomer that is adopted in this method can be made by glucose, is the monomer of biogenetic derivation.But the open loop method that remains that this method adopts is carried out copolymerization, and is higher to the rac-Lactide purity requirement, increased production cost; On the other hand, what this method obtained is random copolymers, and crystal property is relatively poor.In addition, the Tg that improves POLYACTIC ACID can also adopt POLYACTIC ACID and other to have polyester or the polycarbonate generation transesterification reaction formation segmented copolymer of higher Tg.Chinese patent CN200580024916 discloses has aliphatic polycarbonate unit and the unitary aliphatic polyester-carbonate copolymer of aliphatic polyester; Wherein the aliphatic polycarbonate unit can be for derived from the structure of gathering the Isosorbide carbonic ether, and the aliphatic poly ester units can be the structure derived from lactic acid.This patent discloses two kinds of methods that prepare above-mentioned multipolymer; Wherein a kind of method adopts POLYACTIC ACID and Isosorbide carbonate polymer to carry out transesterification reaction as starting raw material exactly and obtains segmented copolymer, and wherein block length depends on the degree of transesterification reaction.But the molecular weight of the multipolymer that this method obtains is explained at high-molecular weight reactant molecular weight in ester-exchange reaction significantly to descend far below the molecular weight of arbitrary starting polymer, thereby is made this method on producing, not have economy.The another kind of method of describing among the CN200580024916 is to form segmented copolymer through being aggregated to the cyclic dimer of hydroxycarboxylic acid on the Isosorbide polycarbonate through ring-opening polymerization; The molecular weight of product that this method obtains is lower; Adopted the ring-opening polymerization method that the cyclic dimer of hydroxycarboxylic acid is carried out polymerization simultaneously, cost is higher.
Above-mentioned true the demonstration is comonomer with the biogenetic derivation material, and the POLYACTIC ACID carbonate copolymer that adopts the lower cost preparation to have sufficiently high thermotolerance and molecular weight does not have report as yet.
Summary of the invention
Monomer is problems such as abiotic source, production cost are higher, the gained molecular weight of copolymer is lower among the copolymer of poly lactic acid preparation method with higher Tg to having now, and the invention discloses a kind of is that catalyzer carries out the polymerization process that polycondensation prepares copolymer of poly lactic acid to lactic acid or lactic acid prepolymer, polycarbonate prepolymer and functional group's regulator with sulfuric acid, sulfonic acid or sulfonic acid/metallic compound compound system.Preparing copolymer of poly lactic acid through present method, to have monomer be that biogenetic derivation, production cost are lower, products therefrom has advantages such as HMW, high Tg simultaneously.
On the other hand, to having problems such as the copolymer of poly lactic acid production cost with higher Tg is higher, molecular weight is lower now, the present invention provides a kind of polycarbonate unit, di-carboxylic acid unit and unitary copolymer of poly lactic acid of POLYACTIC ACID of comprising.This multipolymer have that the preparation method is simple, cost is lower, molecular weight is higher and Tg than advantages such as height.
The object of the invention can reach through following measure:
The preparation method of copolymer of poly lactic acid:
A kind of preparation method of copolymer of poly lactic acid; It is catalyzer that this preparation method includes with sulfuric acid, sulfonic acid or sulfonic acid/metallic compound compound system, to lactic acid or lactic acid prepolymer, carry out the polymerization process that polycondensation prepares copolymer of poly lactic acid with polycarbonate prepolymer and functional group's regulator; Wherein, functional group's regulator is di-carboxylic acid or dicarboxylic acid anhydride.
Employed lactic acid prepolymer can be linear chain structure, also can be structure, star structure or the tridimensional network that has side chain among the preparation method of copolymer of poly lactic acid of the present invention.Can use suitable branching agent to have the lactic acid prepolymer of structure, star structure or the tridimensional network of side chain with acquisition.
Polycarbonate prepolymer described in the preparation method of copolymer of poly lactic acid of the present invention can be the aliphatic polycarbonate prepolymer, also can be the aromatic copolycarbonate prepolymer, can also be the combination of the two.Be preferably the aliphatic polycarbonate prepolymer, further preferably by 1,4:3; 6-two dehydration-D-sorbyl alcohols, 1,4:3,6-two dehydration-D-N.F,USP MANNITOL or 1; 4:3, the polycarbonate prepolymer that one or more in the 6-two dehydration-L-iditols come with the carbonate precursor preparation.Wherein 1,4:3,6-two dehydration-D-sorbyl alcohols, 1; 4:3,6-two dehydration-D-N.F,USP MANNITOL and 1,4:3; 6-two dehydration-L-iditols are 1; 4:3, three kinds of isomerss with different three-dimensional arrangements of 6-two dewatering hexitols are called Isosorbide, different mannitol and different iditol respectively.Isosorbide is preferred, and its structure is as follows:
Carbonate precursor is to have the compound of the compound reaction of hydroxyl with the formation carbonic acid ester bond with two molecules, and its general formula is as follows:
Wherein X and Y can be same base group, also can be different groups.X or Y can be halogen, alkoxyl group or aryloxy group.When X or Y are halogen, be preferably chlorine or bromine, further be preferably chlorine; When X or Y are alkoxyl group, be preferably the alkoxyl group of (comprising 10) below 10 carbon atoms, further be preferably the alkoxyl group of (comprising 6) below 6 carbon atoms; When X or Y are aryloxy, be preferably the aryloxy below 12 carbon atoms.Specifically, suitable carbonate precursor has phosgene, methylcarbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate or phenyl chloroformate.Above-mentioned carbonate precursor can use separately, also can use with the form of above-mentioned two or more mixtures.
Employed polycarbonate prepolymer can add auxiliary agents such as appropriate molecular amount regulator, branching agent or other properties-correcting agent in addition through the preparation of methods such as conventional solution method or scorification among the preparation method of copolymer of poly lactic acid of the present invention.
As the molecular weight regulator that uses among the present invention, can enumerate diisocyanate compound, diacid chloride compounds etc.As the concrete example of molecular weight regulator, can enumerate 1,6-hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, oxalyl chloride, succinic chloride, glutaryl chlorine, hexanedioyl chlorine, sebacoyl chloride, terephthalyl chloride etc.
As the branching agent that uses among the present invention, can enumerate functionality more than or equal to 3 multicomponent alcoholics compound, polycarboxylic acid compounds, polycarboxylic acid compound anhydride or multi-hydroxy acid compounds etc.As the concrete example of branching agent, can enumerate USP Kosher, Pyromellitic Acid, pyromellitic dianhydride, Hydrocerol A, tartrate etc.
As properties-correcting agent, can enumerate hydrolysis-resisting agent, inhibitor, anti-photooxidation agent etc.Concrete example as properties-correcting agent; Can enumerate sodium hydrogencarbonate as hydrolysis-resisting agent, pyrimidine, didecylamine, 2-amino-4-methoxyl group-6-methylpyrimidine, hexanediamine, three normal hexyl Amines etc.; Concrete example as inhibitor; Can enumerate 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, 2; 2-methylene-bis (4; The 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, 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), lauryl thiodipropionates, two-tridecyl thiodipropionate, myristyl thiodipropionate, two octadecyl thiodipropionate, tetramethylolmethane-four (3-lauryl thiopropionate) etc.
Employed polycarbonate prepolymer can be linear chain structure, also can be structure, star structure or the tridimensional network that has side chain among the preparation method of copolymer of poly lactic acid of the present invention.Said in addition polycarbonate prepolymer can be a homopolymer, also can be multipolymer, further can be in random copolymers, alternating copolymer, segmented copolymer or the graft copolymer any one.
The molecular weight of employed polycarbonate prepolymer is not special among the preparation method of copolymer of poly lactic acid of the present invention limits.But consider the thermotolerance and the mechanical property of gained copolymer of poly lactic acid, preferably its weight-average molecular weight is 1000 to 20000, further is preferably 2000 to 10000.
The second-order transition temperature of employed polycarbonate prepolymer is 100 ℃ to 300 ℃ among the preparation method of copolymer of poly lactic acid of the present invention, is preferably 120 ℃ to 250 ℃.
Terminal group for polycarbonate prepolymer among the preparation method of copolymer of poly lactic acid of the present invention does not have special qualification, but considers the reactive behavior of polycarbonate prepolymer, is preferably the polycarbonate prepolymer that end group is a hydroxyl.
Employed functional group regulator is di-carboxylic acid or dicarboxylic acid anhydride among the preparation method of copolymer of poly lactic acid of the present invention.Consider reactive behavior and to the influence of copolymer of poly lactic acid Tg, as the di-carboxylic acid of functional group's regulator or dicarboxylic acid anhydride be preferably the C atomicity less than 16 aliphatic dicarboxylic acid or aliphatic dicarboxylic acid acid anhydride or C atomicity less than 24 aromatic binary carboxylic acid or in the aromatic binary carboxylic acid acid anhydride one or more; Further be preferably terephthalic acid, m-phthalic acid, 1,4-cyclohexyl dicarboxylic acid, 1,4-Succinic Acid, 1,5-pentanedioic acid, 1, one or more in 6-hexanodioic acid, Succinic anhydried, Pyroglutaric acid or the adipic anhydride.Charging capacity for functional group's regulator is confirmed according to the charging capacity and the absolute molecular weight of polycarbonate prepolymer; In fact be exactly to confirm by the quantity of polycarbonate prepolymer institute band edge hydroxyl; Feed ratio is that the molar ratio range of functional group's regulator and polycarbonate prepolymer is 0.8/1～1.2/1 preferably; Consider the molecular weight of multipolymer, preferred molar ratio range is 0.9/1～1.1/1, most preferably is 0.95/1～1.05/1.
The feed ratio of lactic acid described in the preparation method of copolymer of poly lactic acid of the present invention or lactic acid prepolymer and polycarbonate prepolymer can change in a big way, and the feed ratio scope of preferred lactic acid or lactic acid prepolymer and polycarbonate prepolymer is 5/95wt% to 95/5wt%.Usually the higher ingredient proportion of polycarbonate prepolymer will obtain having the multipolymer of higher Tg; Consider the Tg of products therefrom; The feed ratio of further preferred lactic acid or lactic acid prepolymer and polycarbonate prepolymer is 40/60 to 90/10wt%, and more preferably the feed ratio of lactic acid or lactic acid prepolymer and polycarbonate prepolymer is 60/40 to 80/20wt% (condition is that the summation of the weight percent of lactic acid or lactic acid prepolymer and polycarbonate prepolymer is 100%).
To the not special restriction of described sulfonic acid catalyst, can be aromatic sulphonic acid among the preparation method of copolymer of poly lactic acid of the present invention, also can be aliphatic sulfonic, be preferably aliphatic sulfonic; This aliphatic sulfonic catalyzer can be in monobasic sulfonic acid, dibasic sulfoacid or the polybasic sulfoacid one or more, is preferably in dibasic sulfoacid or the polybasic sulfoacid one or more.
Among the preparation method of copolymer of poly lactic acid of the present invention, total add-on of described sulfonic acid is pressed sulfonate radical-SO
3The quality of element sulphur is counted the 0ppm-20000ppm (not comprising 0) of lactic acid or lactic acid prepolymer quality among the H; Consider the mechanical property of product, thermostability, the balance between hydrolytic resistance and the catalytic performance; Be preferably 10-8000ppm; Be preferably 100ppm-5000ppm again, further be preferably 200ppm-4000ppm, that best is 300-3000ppm.
Among the preparation method of copolymer of poly lactic acid of the present invention, the metallic element in the described metallic compound is selected from one or more of metallic element or thulium of IA-IVA family, IB-VIIB family, VIII family, considers catalytic activity, is preferably 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, one or more among the Bi; Consider the thermostability of product, be preferably among Ti, Mn, Fe, Cu, Zn, Al, Ge, Sn, Pb, Sb or the Ce one or more; Further be preferably among Ti, Zn, Sn, Al or the Sb one or more.
Among the preparation method of copolymer of poly lactic acid of the present invention total add-on of described metallic compound counted the 0-200000ppm (not comprising 0) of lactic acid or lactic acid prepolymer quality with the metallic element quality; Consider the mechanical property of product and the balance between the catalytic performance; Be preferably 0-100000ppm (not comprising 0); Better is 10-80000ppm, is preferably 10-30000ppm.
Lactic acid monomer can not done any processing among the preparation method of copolymer of poly lactic acid 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 is meant the physics dehydration, also possibly relate to the condensation dehydration simultaneously.In this treating processes, no matter whether the existence of extra catalyst is arranged, condensation (polycondensation) may inevitably take place.
Prepared copolymer of poly lactic acid can be linear chain structure, also can be structure, star structure or the tridimensional network that has side chain among the preparation method of copolymer of poly lactic acid of the present invention.Resulting in addition copolymer of poly lactic acid can be segmented copolymer, also can be graft copolymer.
Polycondensation can be independent melt polymerization among the preparation method of copolymer of poly lactic acid of the present invention, also can be solid state polymerization, and the combination that can also be both is the method that melt polymerization adds solid state polymerization.
Specifically; Can be reactant with lactic acid, polycarbonate prepolymer and functional group's regulator among the preparation method of copolymer of poly lactic acid of the present invention; Method through melt polymerization is aggregated to lactic acid monomer on the polycarbonate prepolymer and further reaches higher molecular weight through the polycondensation between polycarbonate prepolymer and the functional group's regulator simultaneously and obtains copolymer of poly lactic acid; Perhaps after melt polymerization, make the reactant crystallisation by cooling carry out solid state polymerization again and further improve molecular weight, thereby obtain copolymer of poly lactic acid.On the other hand; Can also be reactant with lactic acid prepolymer, polycarbonate prepolymer and functional group's regulator among the preparation method of copolymer of poly lactic acid of the present invention; Through the method for melt polymerization lactic acid prepolymer, polycarbonate prepolymer and functional group's regulator are carried out polycondensation and obtain copolymer of poly lactic acid; Perhaps after melt polymerization, make the reactant crystallisation by cooling carry out solid state polymerization again and further improve molecular weight, thereby obtain copolymer of poly lactic acid.Can also carry out carrying out crystallization behind simple melt blending or the solution blending to lactic acid prepolymer, polycarbonate prepolymer and functional group's regulator, directly utilize the method for solid state polymerization to obtain the higher copolymer of poly lactic acid of molecular weight.
In the scope of not damaging the object of the invention, can in this polymerization process, add various auxiliary agents, as: inhibitor, photostabilizer, painted suppressor factor or the like.
As the inhibitor that uses among the present invention, can enumerate sterically hindered phenol based compound, bi-ester of phosphite, sulfide compound etc.As the example of 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-pinakon-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 group hexamethylene-diamine, N; N '-tetramethylene-two-3-(3 '-methyl-the 5 '-tertiary butyl-4 '-hydroxyl phenol) propionyl group diamines, N, N '-two-[3-(3,5-di-t-butyl-4-hydroxyl phenol) propionyl group] hydrazine, N-salicylyl-N '-salicylidene hydrazine, 3-(N-salicylyl) amino-1; 2; 4-triazole, N, N '-two [2-{3-(3, the 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 key is attached to 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; Two (4, the 6-di-tert-butyl-phenyl) the octyl group phosphorous acid esters of the inferior different base of 2-, 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 UVNUL MS-40 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 UVNUL MS-40 based compound; Can enumerate UVNUL MS-40,2,4-dihydro UVNUL MS-40,2; 2 '; 4,4 '-tetrahydro-UVNUL MS-40,2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxyl-4; 4 '-dimethoxy-benzophenone, 2; 2 '-dihydroxy benaophenonel, 2-hydroxyl-4-octyloxy UVNUL MS-40,2-hydroxyl-4 dodecyl UVNUL MS-40,2-hydroxyl-4-methoxyl group-5-diphenylsulfone ketone, 5-chloro-2-dihydroxy benaophenonel, 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 UVNUL MS-40 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)-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-Er Jiajibianji) phenyl] benzotriazole, 2-[2 '-hydroxyl-3 ', 5 '-two (α, α-Er Jiajibianji) phenyl]-2H-benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole etc.
As the concrete example of aromatic series phenylformic acid based compound, can enumerate, right-the tert-butyl-phenyl salicylate, right-alkyl phenyl salicylate classes such as 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-cyanic acid-3,3 '-phenylbenzene-propenoate, 2-ethylhexyl-2-cyanic acid-3,3 '-phenylbenzene-propenoate 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-(phenyl acetoxyl group)-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-2,2,6,6-tetramethyl piperidine, 4-cyclohexyloxy-2; 2,6,6-tetramethyl piperidine, 4-benzyloxy-2,2,6,6-tetramethyl piperidine, 4-phenoxy-2,2,6; 6-tetramethyl piperidine, 4-(ethylamino methanoyl)-2,2,6,6-tetramethyl piperidine, 4-(cyclohexyl carboxyamide oxygen base)-2,2,6,6-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)-and adipic acid ester, two (2,2,6,6-tetramethyl--4-piperidyl)-terephthalate, 1, two (2,2,6,6-tetramethyl--4-piperidyl the oxygen)-ethane of 2-, α; α '-two (2,2,6,6-tetramethyl--4-piperidyl oxygen)-right-YLENE, two (2,2,6,6-tetramethyl--4-piperidyl cresylene-2; 4-diurethanes, two (2,2,6,6-tetramethyl--4-piperidyl)-hexa-methylene-1,6-diurethanes, three (2,2,6; 6-tetramethyl--4-piperidyl)-and benzene-1,3,5-tricarboxylic ester, three (2,2,6,6-tetramethyl--4-piperidyl)-benzene-1,3; 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 } 2,2,6,6-tetramethyl piperidine, 1,2; 3,4-BTCA and 1,2,2,6, the 6-pentamethyl--pure and mild β of 4-piperidines, β; β ', β '-tetramethyl--3, the condenses of 9-[2,4,8,10-four oxaspiros (5,5) undecane] terepthaloyl moietie etc.
Copolymer of poly lactic acid:
Obtain a kind of copolymer of poly lactic acid by above-mentioned preparation method, this multipolymer comprises polycarbonate unit, di-carboxylic acid unit and POLYACTIC ACID unit.
Wherein the polycarbonate unit can be the structure of derived from aliphatic polycarbonate, also can be the structure derived from aromatic copolycarbonate, can also be the combination of the two.Be preferably the structure of derived from aliphatic polycarbonate; Further preferably derived from by 1,4:3,6-two dehydration-D-sorbyl alcohols, 1; 4:3; 6-two dehydration-D-N.F,USP MANNITOL or 1,4:3, the structure of the polycarbonate that one or more in the 6-two dehydration-L-iditols come with the carbonate precursor preparation.Wherein 1,4:3,6-two dehydration-D-sorbyl alcohols, 1; 4:3,6-two dehydration-D-N.F,USP MANNITOL and 1,4:3; 6-two dehydration-L-iditols are 1; 4:3, three kinds of isomerss with different three-dimensional arrangements of 6-two dewatering hexitols are called Isosorbide, different mannitol and different iditol respectively.Wherein the polycarbonate unit is preferably the structure of the polycarbonate that comes derived from the preparation of Isosorbide and carbonate precursor, and its structure is as follows:
Carbonate precursor is to have the compound of the compound reaction of hydroxyl with the formation carbonic acid ester bond with two molecules, and its general formula is as follows:
Wherein X and Y can be same base group, also can be different groups.X or Y can be halogen, alkoxyl group or aryloxy group.When X or Y are halogen, be preferably chlorine or bromine, further be preferably chlorine; When X or Y are alkoxyl group, be preferably the alkoxyl group of (comprising 10) below 10 carbon atoms, further be preferably the alkoxyl group of (comprising 6) below 6 carbon atoms; When X or Y are aryloxy, be preferably the aryloxy below 12 carbon atoms.Specifically, suitable carbonate precursor has phosgene, methylcarbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate or phenyl chloroformate.Above-mentioned carbonate precursor can use separately, also can use with the form of above-mentioned two or more mixtures.
Di-carboxylic acid unit in the copolymer of poly lactic acid of the present invention can be the structure of derived from aliphatic di-carboxylic acid; Also can be structure derived from aromatic binary carboxylic acid; Consider the performance of reactive behavior and product, be preferably derived from the C atomicity less than 16 aliphatic dicarboxylic acid or C atomicity, further be preferably derived from terephthalic acid, m-phthalic acid, 1 less than one or more the structure in 24 the aromatic binary carboxylic acid; 4-cyclohexyl dicarboxylic acid, 1; 4-Succinic Acid, 1,5-pentanedioic acid or 1, the structure of one or more in the 6-hexanodioic acid.
POLYACTIC ACID unit described in the copolymer of poly lactic acid of the present invention and the unitary ratio of polycarbonate can change in a big way, and preferred POLYACTIC ACID unit and the unitary part by weight of polycarbonate are 5/95wt% to 95/5wt%.Usually the higher ratio in polycarbonate unit will cause multipolymer to have higher Tg; Consider the Tg of products therefrom; Further preferred POLYACTIC ACID unit and the unitary ratio of polycarbonate are 40/60 to 90/10wt%, and more preferably the unitary ratio of POLYACTIC ACID unit and polycarbonate is 60/40 to 80/20wt% (condition is that the summation of POLYACTIC ACID unit and the unitary weight percent of polycarbonate is 100wt%).
Adopting lactic acid or lactic acid prepolymer, polycarbonate prepolymer and functional group's regulator among the preparation method of copolymer of poly lactic acid of the present invention is reactant, adopts the method polymerization of direct copolycondensation to obtain containing the unitary copolymer of poly lactic acid of polycarbonate.This method is that copolymerization raw material and polycarbonate prepolymer and functional group's regulator carry out direct condensation with lactic acid or lactic acid prepolymer, has avoided the employing rac-Lactide to carry out ring-opening polymerization for the copolymerization raw material, thereby has omitted the link of rac-Lactide purifying, has reduced cost.This method has also adopted the catalyzer of sulfuric acid, sulfonic acid or sulfonic acid/metallic compound compound system as polycondensation, and catalyst system therefor has the advantage of catalytic efficiency (height, catalysis gained multipolymer Heat stability is good.Copolymer of poly lactic acid of the present invention has higher molecular weight, has simultaneously with the POLYACTIC ACID homopolymer to compare high glass transition, can be applied to the field that Blister Package material, disposable foodstuff box etc. are had relatively high expectations to material thermal resistance.In addition, to have monomer be advantages such as biogenetic derivation, production cost are lower to copolymer of poly lactic acid of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is described further, but this does not explain that the present invention only limits to these embodiment.
Explanation for the raw material that the present invention relates to is following:
L-lactic acid: Jiangxi Musashi wildlife chemical industry ltd, the 90wt% aqueous solution.
1,4:3,6-two dehydration-D-sorbyl alcohols (Isosorbide): Alfa easer reagent company
Sulfonic acid and metal catalyst: buy from Sigma-Aldrich Aladdin, Alfa easer, reagent companies such as traditional Chinese medicines
POLYACTIC ACID: NW4032D, Natureworks company
L-rac-Lactide: Tokyo Chemical Industry reagent company
Explanation for the test that the present invention relates to is following:
Weight-average molecular weight (Mw), day island proper Tianjin LCsolution GPC of company, 30 ℃, chromatographic grade trichloromethane leacheate, PS standard.
Second-order transition temperature (Tg), the DSC Q-100 of U.S. TA company.Sample after 2 minutes, is cooled to 0 ℃ 200 ℃ of fusions under the speed of 20 ℃/min, under 0 ℃ of speed with 20 ℃/min, be warmed up to 200 ℃ again.Tg is confirmed by this heating curve.
Preparation example 1:
After injecting the L-lactic acid aqueous solution 200g of 90wt% in the 500mL four-hole boiling flask, flask is put into oil bath.On four-hole boiling flask, install whisking appliance, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline, oil bath temperature is risen to 120 ℃ dewater also with behind the nitrogen replacement 3 times.System pressure progressively is reduced to 5KPa from normal pressure in the dehydration beginning 60 minutes; Under 5KPa, continue dehydration 1.5 hours (amounting to dehydration 2.5 hours) subsequently; At this moment, with nitrogen system pressure is returned to normal pressure after, under nitrogen protection, add stannous acetate 107mg (300ppm) and 1, the 3-third disulfonic acid 363mg (632ppm).System temperature rises to 160 ℃ then, 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 POLYACTIC ACID prepolymer.The apparent productive rate Y% that weighing gets whole polymerization process is 70%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:12000, fusing point Tm:150 ℃, glass transition temperature Tg: 45 ℃.
Preparation example 2:
100g Isosorbide and 500ml pyridine are added in the 1000ml round-bottomed flask, dissolve Isosorbide under the room temperature.Other dropwise drops in the above-mentioned Ismotic under 0 ℃ the dichloromethane solution of the TRIPHOSGENE 99.5 of 300ml 0.76g/mol and stirring 3h under 0 ℃.With 200mlH
2O adds the acid chloride groups of cancellation end group in the above-mentioned reaction system and adds the chloroform component distillation and removes the pyridine in the system.In residual oily matter, add methyl alcohol polymer precipitation is filtered the back with first alcohol and water repeated washing four times.After the filtration, polymkeric substance carries out drying at 50 ℃ in nitrogen atmosphere, obtains the 105.8g polycarbonate prepolymer.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:3857.Glass transition temperature Tg: 124 ℃.
Preparation example 3:
100g Isosorbide and 500ml pyridine are added in the 1000ml round-bottomed flask, dissolve Isosorbide under the room temperature.Other dropwise drops in the above-mentioned Ismotic under 0 ℃ the dichloromethane solution of the TRIPHOSGENE 99.5 of 300ml 0.76g/mol and stirring 10h under 0 ℃.With 200mlH
2O adds the acid chloride groups of cancellation end group in the above-mentioned reaction system and adds the chloroform component distillation and removes the pyridine in the system.In residual oily matter, add methyl alcohol polymer precipitation is filtered the back with first alcohol and water repeated washing four times.After the filtration, polymkeric substance carries out drying at 50 ℃ in nitrogen atmosphere, obtains the 105.8g polycarbonate prepolymer.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:12973.Glass transition temperature Tg: 141 ℃.
Preparation example 4:
100g cyclohexanediol and 500ml pyridine are added in the 1000ml round-bottomed flask, and other dropwise drops in the above-mentioned cyclohexanediol solution under 0 ℃ the dichloromethane solution of the TRIPHOSGENE 99.5 of 300ml0.76g/mol and stirring 10h under 0 ℃.With 200mlH
2O adds the acid chloride groups of cancellation end group in the above-mentioned reaction system and adds the chloroform component distillation and removes the pyridine in the system.In residual oily matter, add methyl alcohol polymer precipitation is filtered the back with first alcohol and water repeated washing four times.After the filtration, polymkeric substance carries out drying at 50 ℃ in nitrogen atmosphere, obtains the 101.6g polycarbonate prepolymer.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:8843.Glass transition temperature Tg: 101 ℃.
Preparation example 5:
With 50g 3; 9-two-(1; 1-dimethyl--2-hydroxyethyl)-2,4,8; 10-four dislikes volution [5.5] undecane and the 300ml pyridine is added in the 1000ml round-bottomed flask, and other dropwise drops in the above-mentioned cyclohexanediol solution under 0 ℃ the dichloromethane solution of the TRIPHOSGENE 99.5 of 300ml 0.76g/mol and stirring 7h under 0 ℃.With 200mlH
2O adds the acid chloride groups of cancellation end group in the above-mentioned reaction system and adds the chloroform component distillation and removes the pyridine in the system.In residual oily matter, add methyl alcohol polymer precipitation is filtered the back with first alcohol and water repeated washing four times.After the filtration, polymkeric substance carries out drying at 50 ℃ in nitrogen atmosphere, obtains the 45.7g polycarbonate prepolymer.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:5632.Glass transition temperature Tg: 107 ℃.
Embodiment 1:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 0.476g1 in synthetic lactic acid prepolymer in the 21g preparation example 1, the 10g preparation example 2, behind the 6-hexanodioic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times; System temperature rises to 160 ℃ then, treats under nitrogen protection, to add tetrabutyl titanate 63mg (add-on is 423ppm in metallic element with respect to the lactic acid prepolymer quality) and 1 after the above-mentioned reactant fusion, and (add-on is with sulfonate radical-SO for the 3-third disulfonic acid 89mg
3Element sulphur quality meter is 1333ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.3KPa and pressure is remained under the 0.3KPa condition melt phase polycondensation and pours out after 4 hours (amounting to 9 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.With particle diameter is the copolymer powder 10g of the 100-250um 1L pyriform bottle back of putting into Rotary Evaporators with nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.After being raised to 110 ℃ in the pyriform bottle immersion silicone oil bath and with oil bath temperature, kept 2 hours.Be warming up to 158 ℃ of solid state polymerizations subsequently 18 hours.Take out powder and obtain copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 69%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:9.2 ten thousand.Glass transition temperature Tg: 81 ℃.
Embodiment 2:
The L-lactic acid aqueous solution that in the 300ml round-bottomed flask, adds 50g90wt%; On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, flask is put into oil bath, system temperature rises to 120 ℃ then; System pressure progressively was reduced to 5KPa from normal pressure in 2 hours lactic acid aqueous solution is carried out processed; Under nitrogen protection, add synthetic polycarbonate prepolymer and 0.162g terephthalic acid in the 3g preparation example 2 after processed is accomplished, treat to add Magnesium Stearate 153mg (add-on is 174ppm in metallic element with respect to the lactic acid quality) and 1 after the above-mentioned reactant fusion, (add-on is with sulfonate radical-SO for the own disulfonic acid 88mg of 6-
3Element sulphur quality meter is 632ppm with respect to the lactic acid quality among the H).Above-mentioned system progressively was reduced to system pressure 0.2KPa and pressure is remained under the 0.2KPa condition melt phase polycondensation and pours out after 4 hours (amounting to 9 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.With particle diameter is the copolymer powder 10g of the 100-250um 1L pyriform bottle back of putting into Rotary Evaporators with nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.After being raised to 110 ℃ in the pyriform bottle immersion silicone oil bath and with oil bath temperature, kept 2 hours.Be warming up to 158 ℃ of solid state polymerizations subsequently 18 hours.Take out powder and obtain copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 70%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:13.4 ten thousand.Glass transition temperature Tg: 62 ℃.
Embodiment 3:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 3.846g1 in synthetic lactic acid prepolymer in the 10g preparation example 1, the 100g preparation example 2, behind the 4-Succinic Acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times; System temperature rises to 160 ℃ then, treats under nitrogen protection, to add four cerium sulfate hydrate 157mg (add-on is 5441ppm in metallic element with respect to the lactic acid prepolymer quality) and 1 after the above-mentioned reactant fusion, and (add-on is with sulfonate radical-SO for 5-naphthalene disulfonic acid 23mg
3Element sulphur quality meter is 632ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.3KPa and pressure is remained under the 0.3KPa condition melt phase polycondensation and pours out after 4 hours (amounting to 9 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.With particle diameter is the copolymer powder 50g of the 100-250um 1L pyriform bottle back of putting into Rotary Evaporators with nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.After being raised to 110 ℃ in the pyriform bottle immersion silicone oil bath and with oil bath temperature, kept 2 hours.Be warming up to 158 ℃ of solid state polymerizations subsequently 18 hours.Take out powder and obtain copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 70%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:4.1 ten thousand.Glass transition temperature Tg: 118 ℃.
Embodiment 4:
The L-lactic acid aqueous solution that in the 300ml round-bottomed flask, adds 50g90wt%; On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, flask is put into oil bath, system temperature rises to 120 ℃ then; System pressure progressively was reduced to 5KPa from normal pressure in 2 hours lactic acid aqueous solution is carried out processed; Processed is accomplished the back and under nitrogen protection, is added synthetic polycarbonate prepolymer and 0.256g1 in the 15.4g preparation routine 3, the 5-pentanedioic acid, and (add-on is with sulfonate radical-SO to treat after the above-mentioned reactant fusion adding aluminum oxide 1971mg (add-on is 28974ppm in metallic element with respect to the lactic acid quality) and methylene-sulfonic acid 793mg
3Element sulphur quality meter is 8000ppm with respect to the lactic acid quality among the H).Above-mentioned system progressively was reduced to system pressure 0.3KPa and pressure is remained under the 0.3KPa condition melt phase polycondensation and pours out after 4 hours (amounting to 9 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.With particle diameter is the copolymer powder 20g of the 100-250um 1L pyriform bottle back of putting into Rotary Evaporators with nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.After being raised to 110 ℃ in the pyriform bottle immersion silicone oil bath and with oil bath temperature, kept 2 hours.Be warming up to 158 ℃ of solid state polymerizations subsequently 18 hours.Take out powder and obtain copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 71%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:8.7 ten thousand.Glass transition temperature Tg: 80 ℃.
Embodiment 5:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 0.551g1 in synthetic lactic acid prepolymer in the 10g preparation example 1, the 30g preparation example 3, behind the 6-hexanodioic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times; System temperature rises to 160 ℃ then, treats under nitrogen protection, to add two hydration manganous acetate 764mg (add-on is 15654ppm in metallic element with respect to the lactic acid prepolymer quality) and 1 after the above-mentioned reactant fusion, and (add-on is with sulfonate radical-SO for the 3-third disulfonic acid 225mg
3Element sulphur quality meter is 7050ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.3KPa and pressure is remained under the 0.3KPa condition melt phase polycondensation and pours out after 12 hours (amounting to 17 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 67%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:5.1 ten thousand.Glass transition temperature Tg: 97 ℃.
Embodiment 6:
In the 300ml round-bottomed flask, add in synthetic lactic acid prepolymer in the 50g preparation example 1, the 48g preparation example 2 behind the synthetic polycarbonate prepolymer and 1.565g Succinic anhydried, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times, system temperature rises to 160 ℃ then, treats under nitrogen protection, to add 5-hydroxyl-1 after the above-mentioned reactant fusion; 3, (add-on is with sulfonate radical-SO for 7-dodecyl trisulfonic acid 893mg
3Element sulphur quality meter is 4025ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to 0.3KPa from normal pressure with system pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, pour out after 5 hours (amounting to 25 hours) at (corresponding in order pressure at each temperature is 0.3KPa, 0.2KPa, 0.1KPa and 0.1KPa) each melt polymerization under 160,180,200 and 220 ℃ subsequently and obtain copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 66%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:7.6 ten thousand.Glass transition temperature Tg: 85 ℃.
Embodiment 7:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 3.646g1 in synthetic lactic acid prepolymer in the 11g preparation example 1, the 65g preparation example 2, behind the 4-cyclohexyl dicarboxylic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, system temperature rises to 160 ℃ then, and (add-on is with sulfonate radical-SO to treat after the above-mentioned reactant fusion under nitrogen protection adding sulfuric acid 18mg
3Element sulphur quality meter is 533ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to 0.3KPa from normal pressure with system pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, pour out after 6 hours (amounting to 23 hours) at (corresponding in order pressure at each temperature is 0.3KPa, 0.2KPa and 0.1KPa) each melt polymerization under 160,180 and 200 ℃ subsequently and obtain copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 67%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:74.7 ten thousand.Glass transition temperature Tg: 105 ℃.
Embodiment 8:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 1.516g1 in synthetic lactic acid prepolymer in the 36g preparation example 1, the 70g preparation example 3, behind the 4-cyclohexyl dicarboxylic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times; System temperature rises to 160 ℃ then, treats under nitrogen protection, to add zinc chloride 13mg (add-on is 174ppm in metallic element with respect to the lactic acid prepolymer quality) and 1 after the above-mentioned reactant fusion, and (add-on is with sulfonate radical-SO for the 3-third disulfonic acid 61mg
3Element sulphur quality meter is 533ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.3KPa and pressure is remained under the 0.3KPa condition melt phase polycondensation and pours out after 20 hours (amounting to 25 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 71%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:5.7 ten thousand.Glass transition temperature Tg: 90 ℃.
Embodiment 9:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 1.083g1 in synthetic lactic acid prepolymer in the 36g preparation example 1, the 50g preparation example 3, behind the 4-cyclohexyl dicarboxylic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times; System temperature rises to 160 ℃ then, treats under nitrogen protection, to add antimony acetate 3mg (add-on is 12ppm in metallic element with respect to the lactic acid prepolymer quality) and 1 after the above-mentioned reactant fusion, and (add-on is with sulfonate radical-SO for the 3-third disulfonic acid 5mg
3Element sulphur quality meter is 15ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.3KPa and pressure is remained under the 0.3KPa condition melt phase polycondensation and pours out after 4 hours (amounting to 9 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.With particle diameter is the copolymer powder 50g of the 100-250um 1L pyriform bottle back of putting into Rotary Evaporators with nitrogen replacement 2 times, in 60 minutes, pressure is dropped to 0.2KPa.After being raised to 110 ℃ in the pyriform bottle immersion silicone oil bath and with oil bath temperature, kept 2 hours.Be warming up to 158 ℃ of solid state polymerizations subsequently 18 hours.Take out powder and obtain copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 73%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:3.2 ten thousand.Glass transition temperature Tg: 69 ℃.
Embodiment 10:
In the 300ml round-bottomed flask, add in synthetic lactic acid prepolymer in the 80g preparation example 1, the 25g preparation example 3 behind the synthetic polycarbonate prepolymer and 0.522g m-phthalic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times; System temperature rises to 160 ℃ then, and (add-on is with sulfonate radical-SO to treat under nitrogen protection, to add after the above-mentioned reactant fusion antimony chloride 205mg (add-on is 2143ppm in metallic element with respect to the lactic acid prepolymer quality) and ethionic acid 150mg
3Element sulphur quality meter is 632ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.3KPa and pressure is remained under the 0.3KPa condition melt phase polycondensation and pours out after 20 hours (amounting to 25 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 71%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:8.9 ten thousand.Glass transition temperature Tg: 79 ℃.
Embodiment 11:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 1.904g1 in synthetic lactic acid prepolymer in the 63g preparation example 1, the 40g preparation example 2, behind the 6-hexanodioic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline also with behind the nitrogen replacement 3 times; System temperature rises to 160 ℃ then, treats under nitrogen protection, to add stannous acetate 40mg (add-on is 317ppm in metallic element with respect to the lactic acid prepolymer quality) and 1 after the above-mentioned reactant fusion, and (add-on is with sulfonate radical-SO for the 3-third disulfonic acid 107mg
3Element sulphur quality meter is 533ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.3KPa and pressure is remained under the 0.3KPa condition melt phase polycondensation and pours out after 20 hours (amounting to 25 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 69%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:8.4 ten thousand.Glass transition temperature Tg: 83 ℃.
Embodiment 12:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 1.523g1 in synthetic lactic acid prepolymer in the 36g preparation example 1, the 32g preparation example 2, behind the 6-hexanodioic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, system temperature rises to 160 ℃ then, and (add-on is with sulfonate radical-SO to treat after the above-mentioned reactant fusion under nitrogen protection adding sulfuric acid 118mg
3Element sulphur quality meter is 1066ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.2KPa and pressure is remained under the 0.2KPa condition melt phase polycondensation and pours out after 10 hours (amounting to 15 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 69%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:9.1 ten thousand.Glass transition temperature Tg: 84 ℃.
Embodiment 13:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 0.602g1 in synthetic lactic acid prepolymer in the 36g preparation example 1, the 32g preparation example 4, behind the 6-hexanodioic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, system temperature rises to 160 ℃ then, and (add-on is with sulfonate radical-SO to treat after the above-mentioned reactant fusion under nitrogen protection adding sulfuric acid 118mg
3Element sulphur quality meter is 1066ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.2KPa and pressure is remained under the 0.2KPa condition melt phase polycondensation and pours out after 10 hours (amounting to 15 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 70%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:6.8 ten thousand.Glass transition temperature Tg: 67 ℃.
Embodiment 14:
In the 300ml round-bottomed flask, add synthetic polycarbonate prepolymer and 0.925g1 in synthetic lactic acid prepolymer in the 36g preparation example 1, the 32g preparation example 5, behind the 6-hexanodioic acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, system temperature rises to 160 ℃ then, and (add-on is with sulfonate radical-SO to treat after the above-mentioned reactant fusion under nitrogen protection adding sulfuric acid 118mg
3Element sulphur quality meter is 1066ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.2KPa and pressure is remained under the 0.2KPa condition melt phase polycondensation and pours out after 10 hours (amounting to 15 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 68%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:5.9 ten thousand.Glass transition temperature Tg: 67 ℃.
Comparative example 1:
In the 300ml round-bottomed flask, add 12g Isosorbide, 18g diphenyl carbonate and 59g rac-Lactide, add the 108mg stannous acetate simultaneously and mix fully.Reaction system with N2 displacement 3 times, under atmospheric pressure with reaction mass heated to 180 ℃, and was kept 30 minutes, then 180 ℃ with the heating 1 hour down of the pressure of 13.3KPa, reheat 30 minutes under the pressure of 180 ℃ and 7.3KPa then.Then temperature is increased to 210 ℃, and under the pressure of this temperature and 0.7KPa, kept 1 hour.Product is poured out cooling obtain copolymer of poly lactic acid.Through product is tested, obtain following salient features:
Weight-average molecular weight Mw:1.7 ten thousand.Glass transition temperature Tg: 71 ℃.
Comparative example 2:
106g Isosorbide, 80ml acetonitrile and 120ml pyridine are added in the 500ml round-bottomed flask, dissolve Isosorbide under the room temperature.In addition the 74g carbonyl chloride is dropwise dropped under 50 ℃ in the above-mentioned Ismotic and at 50 ℃ and stir 3h down.After carbonyl chloride feeds intake and finishes, 400ml acetonitrile and 45ml methyl alcohol are added the acid chloride groups of dilution in the above-mentioned reaction system and cancellation end group, make reactant qualitative change muddiness simultaneously.Above-mentioned RM is poured into precipitation polymers in the 3L water that has added the 150ml1N-aqueous hydrochloric acid.Filter back water and methyl alcohol repeated washing several times.After the filtration, polymkeric substance carries out drying at 50 ℃ in nitrogen atmosphere, obtains the 105g aliphatic polycarbonate.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:1.5 ten thousand.Glass transition temperature Tg: 159 ℃.
After adding the above-mentioned polycarbonate prepolymer of 20g, 37gL-rac-Lactide in the 300ml round-bottomed flask, flask is put into oil bath.On flask, install whisking appliance, insert thermocouple thermometer, connect vacuum pipe and nitrogen pipeline and, under 25/800Pa, keep 3h, using N with behind the nitrogen replacement 3 times
2Recover behind the normal pressure at N
2In system temperature is risen to 220 ℃, treat under nitrogen protection, to add after the above-mentioned reactant fusion stannous octoate 23mg.Above-mentioned system is at 220 ℃/normal pressure N
2Atmosphere is poured out behind the reaction 5h down, and cooling obtains copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 76%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:2.4 ten thousand.Glass transition temperature Tg: 62 ℃.
Comparative example 3:
106g Isosorbide and 500ml pyridine are added in the 1000ml round-bottomed flask, dissolve Isosorbide under the room temperature.In addition the 89g carbonyl chloride is dropwise dropped under 50 ℃ in the above-mentioned Ismotic and at 50 ℃ and stir 10h (increase according to RM viscosity in the reaction process can add the pyridine dilution, adds pyridine 100ml altogether) down.After carbonyl chloride feeds intake and finishes, 700ml chloroform and 100ml methyl alcohol are added in the above-mentioned reaction system the also acid chloride groups of cancellation end group of dilution.RM poured into be settled out polymkeric substance and filtered and recycled polymkeric substance in the 4L methyl alcohol.Polymkeric substance that reclaims and 1000ml0.5N-aqueous hydrochloric acid be added in the 2L beaker also at room temperature stirred 30 minutes.After the filtration, resulting polymers is with 1000ml methanol wash three times.After the filtration, polymkeric substance carries out drying at 50 ℃ in nitrogen atmosphere, obtains the 101g aliphatic polycarbonate.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:6.8 ten thousand.Glass transition temperature Tg: 170 ℃.
In the 500ml round-bottomed flask, add 36g POLYACTIC ACID (NW4032D, Mw=19.8 ten thousand), the above-mentioned polycarbonate of 24g and 120g1,3-dimethyl--2-imidazolone is put into oil bath with flask.On flask, install whisking appliance and the reflux that 30g molecular sieve filtering layer is housed; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline and, then internal pressure is reduced to 8KPa, after system temperature rises to 140 ℃ behind the maintenance 3h with nitrogen replacement 3 times; Under nitrogen protection, add stannous octoate 1.02g, reaction 18h under 140 ℃/8KPa.Above-mentioned RM is poured in the 1L beaker, with making the reactant qualitative change muddy with 45ml methyl alcohol after the 400ml dilution in acetonitrile.Above-mentioned RM is poured into precipitation polymers in the 3L water that has added 150ml 1N-aqueous hydrochloric acid.Filter back water and methyl alcohol repeated washing several times.After the filtration, polymkeric substance carries out drying at 50 ℃ in nitrogen atmosphere, obtains the 47g copolymer of poly lactic acid.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:4.3 ten thousand.Glass transition temperature Tg: 87 ℃.
Comparative example 4:
In the 300ml round-bottomed flask, add in synthetic lactic acid prepolymer in the 36g preparation example 1, the 32g preparation example 2 behind the synthetic polycarbonate prepolymer, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, system temperature rises to 160 ℃ then, and (add-on is with sulfonate radical-SO to treat after the above-mentioned reactant fusion under nitrogen protection adding sulfuric acid 118mg
3Element sulphur quality meter is 1066ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to system pressure 0.2KPa and pressure is remained under the 0.2KPa condition melt phase polycondensation and pours out after 10 hours (amounting to 15 hours) from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h, cooling obtains copolymer of poly lactic acid.The apparent productive rate Y% that weighing gets whole polymerization process is 69%.Through the product sample is tested, obtain following salient features:
Weight-average molecular weight Mw:0.9 ten thousand.Glass transition temperature Tg: 69 ℃.
Comparative example 5:
In the 300ml round-bottomed flask, add in synthetic lactic acid prepolymer in the 36g preparation example 1, the 32g preparation example 2 behind the synthetic polycarbonate prepolymer and 0.804g Pyromellitic Acid, flask is put into oil bath.On flask, install whisking appliance; Insert thermocouple thermometer; Connect vacuum pipe and nitrogen pipeline and with behind the nitrogen replacement 3 times, system temperature rises to 160 ℃ then, and (add-on is with sulfonate radical-SO to treat after the above-mentioned reactant fusion under nitrogen protection adding sulfuric acid 118mg
3Element sulphur quality meter is 1066ppm with respect to the lactic acid prepolymer quality among the H).Above-mentioned system progressively was reduced to 0.2KPa with system pressure and pressure is remained on melt phase polycondensation 5 hours (amounting to 10 hours) after fixing under the 0.2KPa condition, ℃ this still not fusion of multipolymer of rising system temperature to 240 from normal pressure in 2 hours after the N2 of 25L/h flows down reaction 3h.This multipolymer also is insoluble in the organic solvents such as THF, chloroform simultaneously.
Claims (12)
1. the preparation method of a copolymer of poly lactic acid; It is characterized in that: it is catalyzer that this preparation method includes with sulfuric acid, sulfonic acid or sulfonic acid/metallic compound compound system, to lactic acid or lactic acid prepolymer, carry out the polymerization process that polycondensation prepares copolymer of poly lactic acid with polycarbonate prepolymer and functional group's regulator; Wherein, functional group's regulator is di-carboxylic acid or dicarboxylic acid anhydride.
2. the preparation method of copolymer of poly lactic acid according to claim 1; It is characterized in that: described polycarbonate prepolymer is by 1,4:3,6-two dehydration-D-sorbyl alcohols, 1; 4:3; 6-two dehydration-D-N.F,USP MANNITOL or 1,4:3, one or more in the 6-two dehydration-L-iditols and carbonate precursor preparation.
3. the preparation method of copolymer of poly lactic acid according to claim 1 and 2, it is characterized in that: the end group of described polycarbonate prepolymer is a hydroxyl.
4. the preparation method of copolymer of poly lactic acid according to claim 1 and 2 is characterized in that: described carbonate precursor be have hydroxyl with two molecules the compound reaction to form the compound of carbonic acid ester bond, its general formula is as follows:
Wherein X and Y can be same base group, also can be different groups; X or Y are halogen, alkoxyl group or aryloxy group.
5. the preparation method of copolymer of poly lactic acid according to claim 1 and 2, it is characterized in that: the feed ratio of described lactic acid or lactic acid prepolymer and polycarbonate prepolymer is 5/95wt% to 95/5wt%.
6. the preparation method of copolymer of poly lactic acid according to claim 1 and 2; It is characterized in that: described di-carboxylic acid is selected from terephthalic acid, m-phthalic acid, 1,4-cyclohexyl dicarboxylic acid, 1,4-Succinic Acid, 1; 5-pentanedioic acid or 1, one or more in the 6-hexanodioic acid; Described dicarboxylic acid anhydride is selected from one or more in Succinic anhydried, Pyroglutaric acid or the adipic anhydride.
7. the preparation method of copolymer of poly lactic acid according to claim 1, it is characterized in that: described sulfonic acid is one or more in dibasic sulfoacid, the polybasic sulfoacid, total add-on of sulfonic acid is with sulfonate radical-SO
3The quality of element sulphur is counted the 10ppm-8000ppm of lactic acid or lactic acid prepolymer quality among the H.
8. according to the preparation method of the copolymer of poly lactic acid described in the claim 1, it is characterized in that: the metallic element in the described metallic compound is selected from one or more among Ti, Zn, Sn, Al or the Sb; Total add-on of metallic compound is counted the 10-30000ppm of lactic acid or lactic acid prepolymer quality with the metallic element quality.
9. copolymer of poly lactic acid by the preparation of the said method of claim 1, it is characterized in that: it comprises polycarbonate unit, di-carboxylic acid unit and POLYACTIC ACID unit.
10. copolymer of poly lactic acid according to claim 9; It is characterized in that: described polycarbonate unit is derived from by 1,4:3,6-two dehydration-D-sorbyl alcohols, 1; 4:3; 6-two dehydration-D-N.F,USP MANNITOL or 1,4:3, the structure of one or more in the 6-two dehydration-L-iditols and the product of carbonate precursor preparation.
11. copolymer of poly lactic acid according to claim 9; It is characterized in that: described di-carboxylic acid unit is derived from terephthalic acid, m-phthalic acid, 1,4-cyclohexyl dicarboxylic acid, 1,4-Succinic Acid, 1; 5-pentanedioic acid or 1, the structure of one or more in the 6-hexanodioic acid.
12. copolymer of poly lactic acid according to claim 9 is characterized in that: the unitary weight ratio of POLYACTIC ACID unit and polycarbonate is 5/95wt% to 95/5wt% in the described copolymer of poly lactic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105843373A CN102485768A (en) | 2010-12-02 | 2010-12-02 | Polycarbonate unit-containing polylactic acid copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105843373A CN102485768A (en) | 2010-12-02 | 2010-12-02 | Polycarbonate unit-containing polylactic acid copolymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102485768A true CN102485768A (en) | 2012-06-06 |
Family
ID=46151343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105843373A Pending CN102485768A (en) | 2010-12-02 | 2010-12-02 | Polycarbonate unit-containing polylactic acid copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102485768A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456565A (en) * | 2022-04-14 | 2022-05-10 | 欧尚元(天津)有限公司 | Carbon dioxide-based polylactic acid copolymer modified cellulose material and preparation method thereof |
| CN114940745A (en) * | 2022-06-09 | 2022-08-26 | 万华化学集团股份有限公司 | Preparation method of polylactic acid with controllable molecular weight |
-
2010
- 2010-12-02 CN CN2010105843373A patent/CN102485768A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456565A (en) * | 2022-04-14 | 2022-05-10 | 欧尚元(天津)有限公司 | Carbon dioxide-based polylactic acid copolymer modified cellulose material and preparation method thereof |
| CN114940745A (en) * | 2022-06-09 | 2022-08-26 | 万华化学集团股份有限公司 | Preparation method of polylactic acid with controllable molecular weight |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5957885B2 (en) | Polylactic acid block copolymer | |
| EP1114095B1 (en) | Nucleating agent for polyesters | |
| CN103025828B (en) | Blend of polylactic acid resin and copolyester resin, and molded product using same | |
| CN102796251B (en) | Biodegradable polyester-polycarbonate multi-block copolymer and preparation method and application thereof | |
| CN104379631A (en) | 2,5-furan dicarboxylic acid-based polyesters prepared from biomass | |
| KR20140138163A (en) | Process for preparing a high molecular weight heteroaromatic polyester or copolyester | |
| CN103339194A (en) | Polyester resin composition and a production method therefor | |
| CN101585913B (en) | Polyester containing dibasic sulfoacid or polybasic sulfoacid and method for preparing polyester by taking dibasic sulfoacid or polybasic sulfoacid as catalyst | |
| CN105199085B (en) | A kind of dimer acid modified poly-succinic acid-butanediol copolyesters and preparation method thereof | |
| JPH08239461A (en) | Aliphatic polyester copolymer and its production | |
| JP5855973B2 (en) | Polyester resin and polyester film using the same | |
| WO2020106511A1 (en) | Bifuran-modified polyesters | |
| CN102485768A (en) | Polycarbonate unit-containing polylactic acid copolymer and preparation method thereof | |
| JP2012046686A (en) | Isosorbide-copolymerized polyester resin and method for producing the same | |
| CN102199279A (en) | Method for preparing poly lactic acid-polyethylene glycol copolymer by using composite catalyst | |
| EP3625283A1 (en) | Polyester copolymer | |
| CN101805498B (en) | Polylactic acid combination containing sulfonic acid compound and nitrogenous organic compound and preparation method thereof | |
| JP4766893B2 (en) | Polymer and production method thereof | |
| JP5050610B2 (en) | Molded product of resin composition with excellent low-temperature characteristics | |
| Zamora et al. | Butylene copolyesters based on aldaric and terephthalic acids. Synthesis and characterization | |
| KR20140042695A (en) | Polyester resin including component from biomass and preparation method of the same | |
| CN101921400B (en) | L-lactic acid/D-lactic acid segmented copolymer composition and preparation method thereof | |
| JP4323079B2 (en) | Alternating copolymer polyester and process for producing the same | |
| CN101407576B (en) | Method for preparing polylactic acid with sulfamic acid compound as catalyst | |
| CN102241816B (en) | Polylactic acid composition containing monosulfonic acid compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120606 |