CN102241810A - Polylactic acid block copolymer and preparation method thereof - Google Patents

Abstract

The invention relates to a polylactic acid block copolymer and a preparation method thereof. A polylactic acid block copolymer of a high-melting polyester is difficult to prepare by the existing method. The polylactic acid block copolymer provided by the invention is a di-block copolymer expressed as A-b-B, wherein A is a single-terminal hydroxyl aromatic polyester block and B is a polylactic acid block. The invention adopts a solution polymerization method as follows: the soluble reactant single-terminal hydroxyl aromatic polyester and an organic solvent of lactide are used as reaction media, a tin salt is used as a catalyst, and the single-terminal hydroxyl aromatic polyester is used as an initiating agent to initiate ring-opening polymerization of the lactide, thereby effectively introducing the polylactic acid block by the method. By the method provided by the invention, the polymerization temperature can be controlled in a range in which the polylactic acid and the lactide can not be degraded or even racemized, thereby effectively inhibiting the occurrence of an ester exchange reaction, ensuring the regularity of chain blocks, and successfully preparing the block copolymer of polylactic acid and polyester including the high-melting aromatic polyester.

Description

A kind of polylactic-acid block copolymer and preparation method

Technical field

The invention belongs to technical field of polymer materials, relate to a kind of polylactic-acid block copolymer, the invention still further relates to this process for polylactic acid block copolymer production.

Technical background

Poly(lactic acid) (PLA) is because the biomass of its material acid source and biological degradability, and processing characteristics similar to general-purpose plastics such as polypropylene, polyethylene and mechanical and physical performance are arranged, and extensively is subjected to people's attention.It has purposes and huge market potential widely, but compares with polyethylene terephthalate aromatic polyesters such as (PET), and poly(lactic acid) is obviously more crisp, and erosion-resisting characteristics is also relatively poor, and this has limited it to a certain extent and has used widely.

People wish to improve by the whole bag of tricks the performance of poly(lactic acid), as by with aromatic polyester melt phase polycondensation or fusion link coupled method, wishing can comprehensive aromatic polyester and the performance of poly(lactic acid).But because melt phase polycondensation need carry out under the high temperature high vacuum condition, long reaction time, transesterification reaction easily takes place, each segment irregularity of arranging in the multipolymer that obtains, racemization reaction often takes place in lactic acid simultaneously, and polylactic acid chain segment mainly exists with amorphous state, and the content of poly(lactic acid) at most also can only reach 30%, biodegradable characteristic (LichengTan etc., J Therm Anal Calorim, 99:269 – 275 in 2010 of material have directly been influenced; Journal of Applied Polymer Science, 108:2171-2179 in 2008).Chinese patent CN101338025A at first introduces long-chain fat family dibasic alcohol in the PET chain, made low-melting modified PET, then under the condition of fusion (140～210 ℃), method with the modified PET and the hydroxyl-terminated polylactic acid oligopolymer of isocyanic ester coupling terminal hydroxy group, made a series of segmented copolymers that contain polylactic acid chain segment, but owing to carry out, what obtain is some mixtures under fusion link coupled condition, be difficult to separate, can not obtain the clear and definite segmented copolymer of structure.

In addition, Chinese patent CN101134807A reacts under 110～180 ℃ temperature range with the method for melt polymerization, is initiator with various low melting point hydroxy-terminated polymer, by causing the rac-Lactide open loop, synthesized and contained hydroxy-terminated polymer segmental polylactic-acid block copolymer.We notice, initiator in this patent all is some low-melting polymkeric substance, some low-melting aromatic polyesters such as some aliphatic polyesters such as poly butylene succinate, polyethylene glycol succinate, poly adipate succinic acid ester and poly terephthalic acid-Succinic Acid-butanediol ester, poly terephthalic acid-hexanodioic acid-butanediol ester, poly-phthalic acid butanediol ester, poly-m-phthalic acid butanediol ester for example are so melt polymerization can carry out under lower temperature.As everyone knows, racemization and degraded can take place in rac-Lactide and poly(lactic acid) under higher temperature.If method with melt polymerization, polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT) and these initiators of polybutylene terephthalate (PBT) of being higher than 220 ℃ terminal hydroxy group with fusing point, go to cause the rac-Lactide ring-opening polymerization, except serious transesterification reaction is arranged, certainly will also can bring raw material rac-Lactide and racemization of reaction product poly(lactic acid) and degraded, so, be difficult to prepare the polylactic-acid block copolymer that contains PET, PTT, these high melting point polyesters of PBT with the method for ring-opening polymerization under the melting condition.

Summary of the invention

First purpose of the present invention is at the above-mentioned state of the art, and a kind of polylactic-acid block copolymer is provided.

Polylactic-acid block copolymer of the present invention is a di-block copolymer, is expressed as A- b-B, bThe expression block.

A is an one-ended hydroxy aromatic polyester block, and structural formula is:

Wherein: R ₁For

,

,

,

In one or more, when being multiple, its proportioning be arbitrarily than; R ₂Be (CH ₂) ₂, (CH ₂) ₃, (CH ₂) ₄, (CH ₂) ₆,

In one or more, when being multiple, its proportioning be arbitrarily than; R ₃For alkyl, contain carbon-carbon double bond unsaturated substituting group, contain the unsaturated substituting group of carbon-carbon triple bond or contain the unsaturated substituting group of phenyl ring.

B is the poly(lactic acid) block, and its structural formula is:

Described poly(lactic acid) block is one or more in Poly-L-lactic acid block, dextrorotation poly(lactic acid) block, the poly-dl-lactide block, when being multiple, its proportioning be arbitrarily than.

Second purpose of the present invention provides this process for polylactic acid block copolymer production.The principle that the present invention can make polylactic-acid block copolymer is: the organic solvent with molten reactant one-ended hydroxy aromatic polyester of energy and rac-Lactide is a reaction media, with the pink salt is catalyzer, the one-ended hydroxy aromatic polyester is an initiator, cause the rac-Lactide ring-opening polymerization, can introduce polylactic acid chain segment effectively by this method.

The invention provides to prepare and comprise single segmented copolymer of planting the configuration poly(lactic acid), comprise the segmented copolymer of two kinds of configuration poly(lactic acid) or comprise the method for the segmented copolymer of three kinds of configuration poly(lactic acid), contain single segmented copolymer of planting the configuration poly(lactic acid) as preparation and adopt step (1)～(3), the segmented copolymer that contains two kinds of configuration poly(lactic acid) as preparation adopts step (1)～(5), and the segmented copolymer that contains three kinds of configuration poly(lactic acid) as preparation adopts step (1)～(7); Its concrete steps are:

Step (1). the preparation of one-ended hydroxy aromatic polyester: under nitrogen protection, ring-type aromatic polyester oligopolymer, monohydroxy-alcohol and pink salt catalyzer are dissolved in the first kind organic solvent of handling through anhydrous and oxygen-free, under 120～180 ℃ of conditions, react, adopt the GPC(gel permeation chromatograph in the reaction process) the monitoring reaction process, stopped reaction after the fignal center of ring-type aromatic polyester oligopolymer disappears; After reaction is finished, be cooled to normal temperature, because at normal temperatures, product is insoluble to reaction solvent, filters and obtains required one-ended hydroxy aromatic polyester.This reaction is with the pink salt catalyzer, is initiator with the monohydroxy-alcohol, causes the corresponding one-ended hydroxy aromatic polyester that the ring-opening polymerization of ring-type aromatic polyester oligopolymer obtains.

Described ring-type aromatic polyester oligopolymer is the ring-type polyethylene terephthalate, the ring-type Poly(Trimethylene Terephthalate), the ring-type polybutylene terephthalate, ring-type poly terephthalic acid hexylene glycol ester, ring-type poly terephthalic acid-1,4-hexanaphthene dimethyl ester, ring-type poly-1, the 4-(ethylene naphthalate), ring-type poly-1,4-naphthalic acid propylene glycol ester, ring-type poly-1,4-naphthalic acid butanediol ester, ring-type poly-1,4-naphthalic acid hexylene glycol ester, ring-type poly-1,4-naphthalic acid-1,4-hexanaphthene dimethyl ester, ring-type poly-1, the 5-(ethylene naphthalate), ring-type poly-1,5-naphthalic acid propylene glycol ester, ring-type poly-1,5-naphthalic acid butanediol ester, ring-type poly-1,5-naphthalic acid hexylene glycol ester, ring-type poly-1,5-naphthalic acid-1,4-hexanaphthene dimethyl ester, ring-type poly-2, the 6-(ethylene naphthalate), ring-type poly-2,6-naphthalic acid propylene glycol ester, ring-type poly-2,6-naphthalic acid butanediol ester, ring-type poly-2,6-naphthalic acid hexylene glycol ester, ring-type poly-2,6-naphthalic acid-1, one or more in the 4-hexanaphthene dimethyl ester; When being multiple, its proportioning be arbitrarily than.

Described first kind organic solvent is orthodichlorobenzene, tetrachloroethane, oil of mirbane, 1,2, one or more in the 4-trichlorobenzene, when being multiple, its proportioning be arbitrarily than.

The concentration of the ring-type aromatic polyester oligopolymer after the dissolving is 0.2～2Kg/L, and the concentration of the monohydroxy-alcohol after the dissolving is smaller or equal to 200g/L, add catalyzer quality be 0.01～1% of reactant ring-type aromatic polyester oligopolymer and monohydroxy-alcohol total mass.

Step (2). with one-ended hydroxy aromatic polyester process vacuum drying, make its moisture content smaller or equal to 20ppm, one-ended hydroxy aromatic polyester after the oven dry and first kind rac-Lactide are dissolved in the first kind organic solvent of handling through anhydrous and oxygen-free under 60～130 ℃, add the pink salt catalyzer again, 60～150 ℃ of reactions down; Adopt the GPC(gel permeation chromatograph in the reaction process) the monitoring reaction process, stopped reaction after the fignal center of first kind rac-Lactide disappears; Reaction is finished postcooling to normal temperature, filters to obtain first kind crude product.

This reaction is in organic solvent, under relatively low temperature of reaction, is catalyzer with the pink salt, is initiator with the one-ended hydroxy aromatic polyester, causes the ring-opening polymerization of first kind rac-Lactide and obtains corresponding polylactic-acid block copolymer.

Described first kind rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, the L-rac-Lactide.

The concentration of the one-ended hydroxy aromatic polyester after the dissolving is smaller or equal to 100g/L, and the concentration of first kind rac-Lactide is smaller or equal to 2Kg/L, add the pink salt catalyzer quality be 0.01～1% of one-ended hydroxy aromatic polyester and first kind rac-Lactide total mass.

Step (3) is dissolved in the first kind crude product of step (2) gained in the second class organic solvent, and the methyl alcohol with 3～5 times of volumes of the second class organic solvent carries out sedimentation again, and filtering drying obtains first kind product.First kind product is to comprise single segmented copolymer of planting the configuration poly(lactic acid).

The described second class organic solvent is a kind of in chloroform, the trifluoracetic acid or both mixtures, and the concentration of the first kind crude product after the dissolving is 50～200g/L.

Step (4) is dissolved in the first kind product and the second class rac-Lactide in the 3rd class organic solvent of handling through anhydrous and oxygen-free, add the pink salt catalyzer again, 30～140 ℃ of reactions down, adopt the GPC(gel permeation chromatograph in the reaction process) the monitoring reaction process, stopped reaction after the fignal center of the second class rac-Lactide disappears; Reaction is finished postcooling to normal temperature, filters to obtain the second class crude product.

This reaction is under the katalysis of pink salt catalyzer, is initiator with first kind product, causes the second class rac-Lactide ring-opening polymerization and makes the aromatic polyester that contains two kinds of configuration poly(lactic acid) and the segmented copolymer of poly(lactic acid).

The described second class rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, the L-rac-Lactide, and different with first kind rac-Lactide type.

Described the 3rd class organic solvent is one or more in methylene dichloride, chloroform, tetracol phenixin, toluene, tetrahydrofuran (THF), orthodichlorobenzene, the tetrachloroethane, when being multiple, its proportioning be arbitrarily than.

The concentration of the first kind product after the dissolving is smaller or equal to 300g/L, and the concentration of the second class rac-Lactide is smaller or equal to 2Kg/L, add the pink salt catalyzer quality be 0.01～1% of the first kind product and the second class rac-Lactide total mass.

Step (5) is dissolved in the second class crude product of step (4) gained in the chloroform, makes that the concentration of the second class crude product is 50～100g/L, and the methyl alcohol with 3～5 times of volumes of chloroform carries out sedimentation again, and filtering drying obtains the second class product; The second class product is the segmented copolymer that comprises two kinds of configuration poly(lactic acid).

Step (6) is dissolved in the second class product and the 3rd class rac-Lactide in the 3rd class organic solvent of handling through anhydrous and oxygen-free, add the pink salt catalyzer again, 30～140 ℃ of reactions down, adopt the GPC(gel permeation chromatograph in the reaction process) the monitoring reaction process, stopped reaction after the fignal center of the 3rd class rac-Lactide disappears; Reaction is finished postcooling to normal temperature, filters to obtain the 3rd class crude product.

This reaction is under the katalysis of pink salt catalyzer, is initiator with the second class product, causes the 3rd class rac-Lactide ring-opening polymerization, makes the aromatic polyester that contains three kinds of configuration poly(lactic acid) and the segmented copolymer of poly(lactic acid).

Described the 3rd class rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, the L-rac-Lactide, and different with the type of the first kind rac-Lactide and the second class rac-Lactide.

The concentration of the second class product after the dissolving is smaller or equal to 300g/L, and the concentration of the 3rd class rac-Lactide is smaller or equal to 2Kg/L, add the pink salt catalyzer quality be 0.01～1% of the second class product and the 3rd class rac-Lactide total mass.

Step (7) is dissolved in the 3rd class crude product of step (6) gained in the chloroform, makes that the concentration of the 3rd class crude product is 50～100g/L, uses the methyl alcohol sedimentation of 3～5 times of volumes of chloroform again, and filtering drying obtains the 3rd class product; The 3rd class product is the segmented copolymer that comprises three kinds of configuration poly(lactic acid).

Pink salt catalyzer described in step (1), (2), (4) and (6) is Sn (Oct) ₂, SnCl ₂, SnCl ₄, SnBr ₂In a kind of.

What the present invention adopted is the method for solution polymerization, promptly will be earlier that one-ended hydroxy aromatic polyester and rac-Lactide are dissolved in certain amount of organic solvent, adding catalyzer again, is that initiator causes the rac-Lactide open loop with the one-ended hydroxy aromatic polyester, makes the segmented copolymer of aromatic polyester and poly(lactic acid).By this method, can be controlled at poly(lactic acid) to polymerization temperature and rac-Lactide is non-degradable in addition can reach not can the scope of racemization in, effectively suppressed the generation of transesterification reaction, guarantee the segmental regularity, successfully made the polyester that comprises dystectic aromatic polyester and the segmented copolymer of poly(lactic acid).

Embodiment

Below in conjunction with embodiment the present invention is described in further detail.

Embodiment 1

Synthesizing of the segmented copolymer of polybutylene terephthalate (PBT) and poly(lactic acid) (PLA).

Step (1). the ring-opening polymerization that ethanol causes ring-type polybutylene terephthalate (CBT) makes the one-ended hydroxy polybutylene terephthalate

Under nitrogen protection, with 10gCBT, 0.5g ethanol and 0.105g Sn (Oct) ₂Put into the reaction flask roasting, that use the chilled 100ml of nitrogen protection that overdoes.Add the 5ml orthodichlorobenzene of handling through anhydrous and oxygen-free with syringe, make that the concentration of CBT is 2Kg/L, concentration of ethanol is 100g/L.Be reflected under 180 ℃ and carry out, finish (fignal center of the no CBT of GPC monitoring) through reaction in 10 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the CBT monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PBT causes the rac-Lactide polymerization.The 50ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add 0.06g one-ended hydroxy PBT and 4gL-rac-Lactide then, add the 2ml tetrachloroethane with syringe; make that the concentration of PBT is 30g/L; the concentration of rac-Lactide is 2Kg/L, is warmed up to 120 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0106 g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 6 hours, stopped reaction, and cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, be dissolved in the 5ml chloroform, make that crude product concentration is 200 g/L, with the sedimentation of 40ml methyl alcohol, filtering drying obtains product, yield 95.8%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=10.1K, M _w=15.2K, PDI=1.51

¹H-NMR: 8.1ppm(PBT block benzene ring hydrogen), 4.5ppm(PBT the hydrogen of two methylene radical that are connected with oxygen on the block,), 2.0ppm(PBT the hydrogen on two methylene radical that link to each other with carbon on the block), 5.1ppm(PLA the hydrogen on the 1.6ppm(PLA block methyl hydrogen on the block methyne)); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _PBT: m _PLA=1:65

¹³C-NMR: 170.0ppm (carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); 167.0ppm(PBT the carbonyl carbon on the block), 133.2ppm(PBT the carbon on the block phenyl ring on 1,4), 129.3ppm(PBT block phenyl ring 2,3, carbon on 5,6), on the 65.4ppm(PBT block in the butylidene structure 1, carbon on 4 two methylene radical), 24.6ppm(PBT the carbon on 2,3 two methylene radical in the butylidene structure on the block), do not see peaks that all the other are produced by transesterify.

DSC: T _m(215 ℃) corresponding to the PBT block, T _m(160 ℃) are corresponding to the PLA block.

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and illustrates that what obtain is segmented copolymer, and in addition, the DSC curve has the fusing point of two different blocks, and what this also obtained from the side is segmented copolymer.

So what this embodiment obtained is the segmented copolymer of polybutylene terephthalate and Poly-L-lactic acid, in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₄, R ₃Be C ₂H ₅-, the B section is the Poly-L-lactic acid block.

Embodiment 2

Synthesizing of Poly(Trimethylene Terephthalate) (PTT) and poly(lactic acid) (PLA) segmented copolymer.

Step (1). the ring-opening polymerization that methyl alcohol causes ring-type Poly(Trimethylene Terephthalate) (CTT) makes the one-ended hydroxy Poly(Trimethylene Terephthalate)

Under nitrogen protection, with 10g CTT, 1.0g methyl alcohol and 0.0011 g SnCl ₂Put into the reaction flask roasting, that use the chilled 100ml of nitrogen protection that overdoes.Add the 5ml tetrachloroethane of handling through anhydrous and oxygen-free with syringe, make that the concentration of CTT is 2Kg/L, the concentration of methyl alcohol is 200g/L.Be reflected under 180 ℃ and carry out, finish (fignal center of the no CTT of GPC monitoring) through reaction in 5 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the CTT monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PTT causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add 0.06g one-ended hydroxy PTT and 1gD-rac-Lactide then, add the 2ml orthodichlorobenzene with syringe again; make that the concentration of PTT is 30g/L; the concentration of rac-Lactide is 0.5Kg/L, is warmed up to 60 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0106g SnCl with syringe again ₂, 60 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 24 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, be dissolved in the 20ml chloroform, make that crude product concentration is 50 g/L, with the sedimentation of 60ml methyl alcohol, filtering drying obtains final product, yield 96.0%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=8.9K, M _w=12.7K, PDI=1.43

¹H-NMR: 8.19ppm(PTT block benzene ring hydrogen), 4.7ppm(PTT block 1,3 propylidene structures 1, the hydrogen of 3 two methylene radical), 2.46ppm(PTT block 1, hydrogen on the 3 propylidene structure intermediate sub methyl), the hydrogen on the 5.1ppm(PLA block methyne), the hydrogen on the 1.6ppm(PLA block methyl); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _PTT: m _PLA=1:16

¹³C-NMR: 170.0ppm (carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); 168.6ppm(PTT the carbonyl carbon on the block), the carbon on 1,4 on the 133.2ppm(PTT block phenyl ring), 129.4ppm(PTT encircle 2 on the block phenyl ring, carbon on 3,5,6), 63.0ppm(PTT block 1, in the 3 propylidene structures on 1,3 methylene radical carbon), 26.8ppm(PTT block 1, the carbon of 2 methylene radical of 3 propylidene structures), do not see the peak that all the other are produced by transesterify.

DSC: T _m(173 ℃) corresponding to the PLA block, T _m(212 ℃) are corresponding to the PTT block

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer

So what this embodiment obtained is the segmented copolymer of Poly(Trimethylene Terephthalate) and dextrorotation poly(lactic acid), in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₃, R ₃Be CH ₃-, the B section is a dextrorotation poly(lactic acid) block.

Embodiment 3

Synthesizing of polyethylene terephthalate (PET) and poly(lactic acid) (PLA) segmented copolymer.

The ring-opening polymerization that step (1) .1-propyl alcohol causes ring-type polyethylene terephthalate (CET) makes the one-ended hydroxy polyethylene terephthalate

Under nitrogen protection, with 10g CET, 0.1g1-propyl alcohol and 0.0101 g SnBr ₂Put into the reaction flask roasting, that use the chilled 100ml of nitrogen protection that overdoes.Add the 50ml oil of mirbane of handling through anhydrous and oxygen-free with syringe, make that the concentration of CET is 0.2Kg/L, the concentration of 1-propyl alcohol is 2g/L.Be reflected under 120 ℃ and carry out, finish (fignal center of the no CET of GPC monitoring) through reaction in 60 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the CET monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PET causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, under protection of nitrogen gas, adds 0.06g one-ended hydroxy PET and 1g D-rac-Lactide then, adds 2mlV with syringe again _{Tetrachloroethane}: V _{Orthodichlorobenzene}The mixed solvent of=1:1 makes that the concentration of PET is 30g/L, and the concentration of rac-Lactide is 0.5Kg/L, is warmed up to 120 ℃, and under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.0106g SnBr with syringe again ₂, 130 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 5 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). add the 20ml chloroform in crude product, make that crude product concentration is 50g/L, with the sedimentation of 100ml methyl alcohol, filtering drying obtains final product, 96.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=23.1K, M _w=31.4K, PDI=1.36

¹H-NMR: 7.97ppm(PET block benzene ring hydrogen), the hydrogen on the 4.67ppm(PET block ethylidene), the hydrogen on the 5.42ppm(PLA block methyne), the hydrogen on the 1.68ppm(PLA block methyl); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _PET: m _PLA=1:16.

¹³C-NMR: 170.0ppm (carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); 168.4ppm(PET the carbonyl on the block), 133.0ppm(PET the carbon that links to each other with carbonyl on the block phenyl ring), 129.5ppm(PET the phenyl ring 2 on the block, 3,4, carbon on 5), the carbon on two methylene radical that are connected with oxygen on the 63.6ppm(PET block ethylidene structure), do not see the peak that all the other are produced by transesterify

DSC: T _m(160 ℃) corresponding to the PLA block, T _m(245 ℃) are corresponding to the PET block

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

So what this embodiment obtained is the segmented copolymer of polyethylene terephthalate and poly(lactic acid), in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₂, R ₃Be C ₃H ₇-, the B section is a dextrorotation poly(lactic acid) block.

Embodiment 4

Poly-2, the synthesizing of 6-naphthalic acid hexylene glycol ester (PHN) and poly(lactic acid) (PLA) segmented copolymer.

Step (1) .1-butanols causes ring-type and gathers 2, and the ring-opening polymerization of 6-naphthalic acid hexylene glycol ester (CHN) makes one-ended hydroxy and gathers 2,6-naphthalic acid hexylene glycol ester

Under nitrogen protection, with 10g CHN, 0.1g1-butanols and 0.0101 g SnCl ₄Put into the reaction flask roasting, that use the chilled 100ml of nitrogen protection that overdoes.Add the 40ml1 that handles through anhydrous and oxygen-free with syringe, 2, the 4-trichlorobenzene makes that the concentration of CHN is 0.25Kg/L, the concentration of 1-butanols is 2.5g/L.Be reflected under 150 ℃ and carry out, finish (fignal center of the no CHN of GPC monitoring) through reaction in 30 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the CHN monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PHN causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, then under protection of nitrogen gas; add 0.1g one-ended hydroxy PHN and 2g D, the L-rac-Lactide adds 10ml1 with syringe again; 2; the 4-trichlorobenzene makes that the concentration of PHN is 10g/L, and the concentration of rac-Lactide is 0.2Kg/L; be warmed up to 130 ℃; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.003g SnCl with syringe again ₄, 150 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 2 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 40ml chloroform, make crude product concentration 50g/L, with the sedimentation of 120ml methyl alcohol, filtering drying obtains final product, yield 97.1%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=65.1K, M _w=101.56K, PDI=1.56

¹H-NMR: the hydrogen on the 8.85ppm(PHN block naphthalene nucleus on 1,5), on the 8.15ppm(PHN block naphthalene nucleus 3, hydrogen on 4,7,8), 4.5ppm(PHN in the block hexylidene 1, hydrogen on 6 two methylene radical), the hydrogen on 3,4 two methylene radical in the 1.7ppm(PHN block hexylidene), 2.05ppm(PHN block hexylidene 2, hydrogen on 5 two methylene radical), the hydrogen on the 5.1ppm(PLA block methyne), the hydrogen on the 1.6ppm(PLA block methyl); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _PHN: m _PLA=1:19.

¹³C-NMR: 167.0ppm (carbonyl carbon on the PHN block), 131.2 the ppm (naphthalene nucleus 1 on the PHN block, carbon on 5), 132.4 the ppm (naphthalene nucleus 2 on the PHN block, carbon on 6), 130.0 the ppm (naphthalene nucleus 3 on the PHN block, carbon on 7), 130.0 the ppm (naphthalene nucleus 4 on the PHN block, carbon on 8), 61.2ppm(PHN in the block hexylidene 1, carbon on 6 two methylene radical), 25.2(PHN in the block hexylidene 2, carbon on 5 two methylene radical), 20.6(PHN in the block hexylidene 3, carbon on 4 two methylene radical), (170.0ppm the carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); Do not see the peak that all the other are produced by transesterify

DSC: T _m(205 ℃) are poly-dl-lactides owing to what generate, so do not see the fusion endotherm(ic)peak of PLA block corresponding to the PHN block.

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is to gather 2, the segmented copolymer of 6-naphthalic acid hexylene glycol ester (PHN) and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₆, R ₃Be C ₄H ₉-, the B section is the poly-dl-lactide block.

Embodiment 5

Poly-2,6-naphthalic acid-1, the synthesizing of 4-hexanaphthene dimethyl ester (PCN) and poly(lactic acid) (PLA) segmented copolymer.

Step (1) .1-nonyl alcohol causes ring-type and gathers 2,6-naphthalic acid-1, and the ring-opening polymerization of 4-hexanaphthene dimethyl ester (CCN) makes one-ended hydroxy and gathers 2,6-naphthalic acid-1,4-hexanaphthene dimethyl ester.

Under nitrogen protection, with 10g CCN, 0.1g1-nonyl alcohol and 0.0101 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}The mixed solvent of=1:1 makes that the concentration of CCN is 1.0Kg/L, and the concentration of 1 nonyl alcohol is 10g/L.Be reflected under 170 ℃ and carry out, finish (fignal center of the no CCN of GPC monitoring) through reaction in 10 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the CCN monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PCN causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the one-ended hydroxy PCN and the 2g D-rac-Lactide of 0.1g step (1) gained then, add 10ml oil of mirbane with syringe again; make that the concentration of PCN is 10g/L; the concentration of rac-Lactide is 0.2Kg/L, is warmed up to 100 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.003g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 3 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 40ml chloroform, make that crude product concentration is 52g/L, with the sedimentation of 150ml methyl alcohol, filtering drying obtains final product, yield 97.7%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=21.1K, M _w=34.42K, PDI=1.49

¹H-NMR: on the 8.82ppm(naphthalene nucleus 1, hydrogen on 5), 8.11ppm(on the naphthalene nucleus 3,4,7, hydrogen on 8), 4.4ppm(PCN in the block with 1,4 two continuous methylene radical of cyclohexylidene on hydrogen), the hydrogen on 1.3～2.2ppm(PCN block cyclohexylidene), 5.1ppm(PLA the hydrogen on the 1.6ppm(PLA block methyl hydrogen on the block methyne)); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _PCN: m _PLA=1:19

¹³C-NMR: 168.2ppm (carbonyl carbon on the PCN block), 131.1 the ppm (naphthalene nucleus 1 on the PCN block, carbon on 5), 132.3 the ppm (naphthalene nucleus 2 on the PCN block, carbon on 6), 130.1 the ppm (naphthalene nucleus 3 on the PCN block, carbon on 7), 130.4ppm (the naphthalene nucleus 4 on the PCN block, carbon on 8), 136.1ppm (the naphthalene nucleus 9 on the PCN block, carbon on 10), 61.2ppm(PCN in the block cyclohexylidene 1, carbon on 4 two continuous methylene radical), 25.2 the carbon in the ppm(PCN block cyclohexylidene on 1,4 two methyne), in the 18.6 ppm(PCN block cyclohexylidenes 2,3, carbon on 5,6 four methylene radical), 170.0ppm (carbonyl carbon on the PLA block), 69.2ppm(PLA the carbon on the 15.7ppm(PLA block methyl methine carbon on the block)); Do not see the peak that all the other are produced by transesterify.

DSC: T _m(168 ℃) corresponding to the PLA block, T _m(320 ℃) are corresponding to the PCN block

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is to gather 2,6-naphthalic acid-1, and the segmented copolymer of 4-hexanaphthene dimethyl ester (PCN) and poly(lactic acid), in general formula, the R of A segment structure formula ₁For

, R ₂For

, R ₃Be C ₉H ₁₉-, the B section is a dextrorotation poly(lactic acid) block.

Embodiment 6

Synthesizing of the segmented copolymer of polyethylene glycol 1 and poly(lactic acid) (PLA).

Step (1). the ring-opening polymerization that vinyl carbinol causes the ring-type polyethylene glycol 1 makes the one-ended hydroxy polyethylene glycol 1.

Under nitrogen protection, with 10g ring-type polyethylene glycol 1,0.3g allyl alcohol and 0.0103 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}: V _{Trichlorobenzene}The mixed solvent of=1:1:1 makes that the concentration of ring-type polyethylene glycol 1 is 1.0Kg/L, and the concentration of allyl alcohol is 30g/L.Be reflected under 160 ℃ and carry out, finish (fignal center of GPC monitoring monomer-free) through reaction in 15 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). the one-ended hydroxy polyethylene glycol 1 causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, under protection of nitrogen gas, adds the one-ended hydroxy polyethylene glycol 1 and the 3g D-rac-Lactide of 1g step (1) gained then, adds 20ml V with syringe again _{Tetrachloroethane}: V _{Orthodichlorobenzene}: V _{Oil of mirbane}The mixed solvent of=1:1:1 makes that the concentration of polyethylene glycol 1 is 50g/L, and the concentration of rac-Lactide is 0.15Kg/L, is warmed up to 120 ℃, and under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.02g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 5 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 20ml trifluoracetic acid, make crude product concentration 200g/L, with the sedimentation of 100ml methyl alcohol, filtering drying obtains final product, yield 98.1%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: owing to gather 1 in the multipolymer, the content of 4-(ethylene naphthalate) block is bigger, solvability in chloroform is not very desirable, so be solvent with the ortho chloro phenol earlier, is made into 10mg/mL, be diluted to 1mg/mL with chloroform again, with the volume ratio of chloroform and ortho chloro phenol is that 10 mixed solvent is a moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, wherein collection of illustrative plates presents normal distribution, records M _n=54.1K, M _w=85.48K, PDI=1.58

¹H-NMR: on the 8.75ppm(naphthalene nucleus 2, hydrogen on 3), 8.05ppm(on the naphthalene nucleus 6, hydrogen on 7), 8.55ppm(the hydrogen on two methylene radical in the 4.70ppm(polyethylene glycol 1 hydrogen on the naphthalene nucleus on 5,8)), 5.1ppm(PLA the hydrogen on the 1.6ppm(PLA block methyl hydrogen on the block methyne)); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _{Polyethylene glycol 1}: m _PLA=1:3.

¹³C-NMR: 168.6.0ppm (poly-1, carbonyl carbon on the 4-(ethylene naphthalate) block), 132.7 ppm (poly-1, naphthalene nucleus 1 on the 4-(ethylene naphthalate) block, carbon on 4), 126.9ppm (poly-1, naphthalene nucleus 2 on the 4-(ethylene naphthalate) block, carbon on 3), 131.4 ppm (poly-1, naphthalene nucleus 5 on the 4-(ethylene naphthalate) block, carbon on 8), 127.9ppm (poly-1, naphthalene nucleus 6 on the 4-(ethylene naphthalate) block, carbon on 7), (135.1ppm the naphthalene nucleus on the polyethylene glycol 1 block 9,10 on carbon), 66.7ppm(poly-1, carbon in the 4-(ethylene naphthalate) block ethylidene on two methylene radical), (170.0ppm the carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); Do not see the peak that all the other are produced by transesterify.

DSC: T _m(230 ℃) corresponding to the polyethylene glycol 1 block, T _m(160 ℃) are corresponding to the melting peak of poly(lactic acid)

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is the segmented copolymer of polyethylene glycol 1 and poly(lactic acid), in general formula, and the R of A segment structure formula ₁For , R ₂Be (CH ₂) ₂, R ₃For

, the B section is a dextrorotation poly(lactic acid) block.

 

Embodiment 7

Poly-1,5-(ethylene naphthalate) and poly(lactic acid) (PLA) segmented copolymer synthetic.

Step (1). phenylcarbinol causes ring-type and gathers 1, and the ring-opening polymerization of 5-(ethylene naphthalate) makes one-ended hydroxy and gathers 1, the 5-(ethylene naphthalate).

Under nitrogen protection, the 10g ring-type is gathered 1,5-(ethylene naphthalate), 0.3g benzylated polyol and 0.0103 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}: V _{Trichlorobenzene}: V _{1,2,4 trichlorobenzene}The mixed solvent of=1:1:1:1 makes ring-type gather 1, and the concentration of 5-(ethylene naphthalate) is 1.0Kg/L, and the concentration of benzylated polyol is 30g/L.Be reflected under 150 ℃ and carry out, finish (fignal center of GPC monitoring monomer-free) through reaction in 20 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). one-ended hydroxy gathers 1, and the 5-(ethylene naphthalate) causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, and under protection of nitrogen gas, the one-ended hydroxy that adds 1g step (1) gained gathers 1 then, 5-(ethylene naphthalate) and 1g D, and the L-rac-Lactide adds 20ml V with syringe again _{Tetrachloroethane}: V _{Orthodichlorobenzene}: V _{Oil of mirbane}: V _{1,2,4 trichlorobenzene}The mixed solvent of=1:1:1:1 makes and gathers 1 that the concentration of 5-(ethylene naphthalate) is 50g/L, the concentration of rac-Lactide is 0.05Kg/L, is warmed up to 130 ℃, under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.02g Sn (Oct) with syringe again ₂, 150 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 3 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 20ml trifluoracetic acid, make crude product concentration 100g/L, with the sedimentation of 90ml methyl alcohol, filtering drying obtains final product, yield 98.5%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: owing to gather 1 in the multipolymer, the content of 5-(ethylene naphthalate) block is bigger, solvability in chloroform is not very desirable, so be solvent with the ortho chloro phenol earlier, is made into 10mg/mL, be diluted to 1 mg/mL with chloroform again, with the volume ratio of chloroform and ortho chloro phenol is that 10 mixed solvent is a moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, wherein collection of illustrative plates presents normal distribution, records M _n=65.6K, M _w=106.1K, PDI=1.62

¹H-NMR: on the 8.75ppm(naphthalene nucleus 4, hydrogen on 8), 8.05ppm(on the naphthalene nucleus 2, hydrogen on 3,6,7), 4.71ppm(poly-1, hydrogen in the 5-(ethylene naphthalate) on two methylene radical), the hydrogen on the 5.1ppm(PLA block methyne), the hydrogen on the 1.6ppm(PLA block methyl); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _{Gather 1, the 5-(ethylene naphthalate)}: m _PLA=1:1

¹³C-NMR: 171.0ppm (poly-1, carbonyl carbon on the 5-(ethylene naphthalate) block), 126.9 ppm (poly-1, naphthalene nucleus 1 on the 5-(ethylene naphthalate), carbon on 5), 132.7 ppm (poly-1, naphthalene nucleus 2 on the 5-(ethylene naphthalate) block, carbon on 6), 131.4 ppm (poly-1, naphthalene nucleus 3 on the 5-(ethylene naphthalate) block, carbon on 7), 129.6 ppm (poly-1, naphthalene nucleus 4 on the 5-(ethylene naphthalate) block, carbon on 8), 134.1ppm (poly-1, naphthalene nucleus 9 on the 5-(ethylene naphthalate) block, carbon on 10), 66.7ppm(poly-1, carbon in the 5-(ethylene naphthalate) block ethylidene on two methylene radical), (170.0ppm the carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); Do not see the peak that all the other are produced by transesterify.

DSC: T _m(262 ℃) corresponding to gathering 1,5-(ethylene naphthalate) block is the poly-dl-lactide block owing to what generate, so do not see the melting peak of poly(lactic acid).

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is to gather 1, the segmented copolymer of 5-(ethylene naphthalate) and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For , R ₂Be (CH ₂) ₂, R ₃For

, the B section is the poly-dl-lactide block.

Embodiment 8

Gather 2,6-naphthalic acid-ethylene glycol-hexylene glycol ester (P(EN ₉₀-HN ₁₀)) and the segmented copolymer of poly(lactic acid) (PLA) is synthetic.P(EN wherein ₉₀-HN ₁₀) represent to contain the PEN of 90% molar fraction and the PHN of 10% molar fraction in the copolyesters segment

Step (1). phenylcarbinol causes the ring-type polyethylene glycol 2 and ring-type gathers 2, and the ring-opening polymerization of 6-naphthalic acid hexylene glycol ester makes one-ended hydroxy and gathers 2,6-naphthalic acid-ethylene glycol-hexylene glycol ester.

Under nitrogen protection, be that 9 ring-type polyethylene glycol 2 and ring-type are poly-2 with the 10g mol ratio, 6-naphthalic acid hexylene glycol ester, 0.2g benzylated polyol and 0.0102 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml tetrachloroethane of handling through anhydrous and oxygen-free with syringe, make that the total concn of reaction monomers is 1.0Kg/L, the concentration of benzylated polyol is 20g/L.Be reflected under 180 ℃ and carry out, finish (fignal center of GPC monitoring monomer-free) through reaction in 5 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). the P(EN of one-ended hydroxy ₉₀-HN ₁₀) polymerization of initiation rac-Lactide.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, under protection of nitrogen gas, adds the one-ended hydroxy P(EN of 1g step (1) gained then ₉₀-HN ₁₀) and 3g D, the L-rac-Lactide adds the 10ml tetrachloroethane with syringe again, makes P(EN ₉₀-HN ₁₀) concentration be 100g/L, the concentration of rac-Lactide is 0.3Kg/L, 120 ℃ of dissolvings, under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.0004g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 3 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 40ml trifluoracetic acid, make crude product concentration 100g/L, with the sedimentation of 150ml methyl alcohol, filtering drying obtains final product, yield 97.5%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: because P(EN in the multipolymer ₉₀-HN ₁₀) content of block is bigger, solvability in chloroform is not very desirable, so be solvent with the ortho chloro phenol earlier, being made into 10mg/mL, being diluted to 1 mg/mL with chloroform again, is that 10 mixed solvent is a moving phase with the volume ratio of chloroform and ortho chloro phenol, flow velocity 1.0ml/min, make standard specimen with PS, wherein collection of illustrative plates presents normal distribution, records M _n=25.1K, M _w=39.1K, PDI=1.56

¹H-NMR: 8.85ppm(P(EN ₉₀-HN ₁₀) hydrogen on the block naphthalene nucleus on 1,5), 8.15ppm(P(EN ₉₀-HN ₁₀) hydrogen on the block naphthalene nucleus on 3,4,7,8), 4.5ppm(P(EN ₉₀-HN ₁₀) hydrogen in the block hexylidene on 1,6 two methylene radical), 1.7ppm(P(EN ₉₀-HN ₁₀) hydrogen in the block hexylidene on 3,4 two methylene radical), 2.05ppm(P(EN ₉₀-HN ₁₀) hydrogen on 2,5 two methylene radical of block block hexylidene), 4.67ppm(P(EN ₉₀-HN ₁₀) hydrogen in the block ethylidene on two methylene radical), the hydrogen on the 5.1ppm(PLA block methyne), the hydrogen on the 1.6ppm(PLA block methyl); Do not see that the peak that 6-naphthalic acid-ethylene glycol-hexylene glycol ester and poly-lactic acid ester exchange produce obtains m by integral area by gathering 2 _P(EN90-HN10): m _PLA=1:2.8

¹³C-NMR: 171.0ppm (P(EN ₉₀-HN ₁₀) carbonyl carbon on the block), 126.9 ppm (P(EN ₉₀-HN ₁₀) carbon on 1,5 of the naphthalene nucleus on the block), 132.7 ppm (P(EN ₉₀-HN ₁₀) carbon on 2,6 of the naphthalene nucleus on the block), 131.4 ppm (P(EN ₉₀-HN ₁₀) carbon on 3,7 of the naphthalene nucleus on the block), 129.6 ppm (P(EN ₉₀-HN ₁₀) carbon on 4,8 of the naphthalene nucleus on the block), 66.7ppm(P(EN ₉₀-HN ₁₀) carbon in the block ethylidene on two methylene radical), 131.2 ppm (P(EN ₉₀-HN ₁₀) carbon on 1,5 of the naphthalene nucleus on the block), 132.4 ppm (P(EN ₉₀-HN ₁₀) carbon on 2,6 of the naphthalene nucleus on the block), 130.0 ppm (P(EN ₉₀-HN ₁₀) carbon on 3,7 of the naphthalene nucleus on the block), 130.0 ppm (P(EN ₉₀-HN ₁₀) carbon on 4,8 of the naphthalene nucleus on the block), 61.2ppm(P(EN ₉₀-HN ₁₀) carbon in the block hexylidene on 1,6 two methylene radical), 25.2(P(EN ₉₀-HN ₁₀) carbon in the block hexylidene on 2,5 two methylene radical), 20.6(P(EN ₉₀-HN ₁₀) carbon in the block hexylidene on 3,4 two methylene radical), 170.0ppm (carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); Do not see by gathering 2, the peak that 6-naphthalic acid-ethylene glycol-hexylene glycol ester and poly-lactic acid ester exchange produce.

DSC: T _m(220 ℃) are corresponding to P(EN ₉₀-HN ₁₀) block, be the poly-dl-lactide block owing to what generate, so do not see the melting peak of PLA.

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is to gather 2, the segmented copolymer of 6-naphthalic acid-ethylene glycol-hexylene glycol ester and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₂(CH ₂) ₆, (CH wherein ₂) ₂(CH ₂) ₆Mol ratio be 90:10, R ₃For

, the B section is the poly-dl-lactide block.

Embodiment 9

Poly terephthalic acid-ethylene glycol _80-Propylene glycol ₁₀-butyleneglycol ₁₀Ester (abbreviates PE as ₈₀T ₁₀B ₁₀T, subscript is expressed as molar content, the subscript of dibasic alcohol represents that this kind dibasic alcohol accounts for the molar content of total alcohol) and polylactic-acid block copolymer is synthetic.

Step (1) .1-amylalcohol initiation ring-type polyethylene terephthalate, ring-type Poly(Trimethylene Terephthalate), the ring-opening polymerization of ring-type polybutylene terephthalate make one-ended hydroxy and gather 2,6-naphthalic acid-ethylene glycol-hexylene glycol ester.

Under nitrogen protection, be ring-type polyethylene terephthalate, ring-type Poly(Trimethylene Terephthalate), ring-type polybutylene terephthalate, 0.4g1-amylalcohol and the 0.0104 g Sn (Oct) of 8:1:1 with the 10g mol ratio ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 5ml tetrachloroethane of handling through anhydrous and oxygen-free with syringe, make that the total concn of reaction monomers is 2.0Kg/L, the concentration of 1-amylalcohol is 20g/L.Be reflected under 170 ℃ and carry out, finish (fignal center of GPC monitoring monomer-free) through reaction in 10 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PE ₈₀T ₁₀B ₁₀T causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, under protection of nitrogen gas, adds the one-ended hydroxy PE of 1g step (1) gained then ₈₀T ₁₀B ₁₀T and 3g D, the L-rac-Lactide adds the 10ml tetrachloroethane with syringe again, makes PPE ₈₀T ₁₀B ₁₀The concentration of T is 100g/L, and the concentration of rac-Lactide is 0.3Kg/L, is warmed up to 120 ℃, and under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.04g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 3 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 20ml trifluoracetic acid, make crude product concentration 200g/L, with the sedimentation of 100ml methyl alcohol, filtering drying obtains final product, yield 93.5%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: because the content of aromatic copolyester block is bigger in the multipolymer, solvability in chloroform is not very desirable, so be solvent with the ortho chloro phenol earlier, being made into 10mg/mL, being diluted to 1 mg/mL with chloroform again, is that 10 mixed solvent is a moving phase with the volume ratio of chloroform and ortho chloro phenol, flow velocity 1.0ml/min, make standard specimen with PS, wherein collection of illustrative plates presents normal distribution, records M _n=30.9K, M _w=42.02K, PDI=1.36

¹H-NMR: ¹H-NMR: 8.1ppm(PBT block benzene ring hydrogen), 4.65ppm(the hydrogen of two methylene radical that are connected with oxygen on the aromatic polyester block,), 2.0ppm(the hydrogen on the prosposition on 1,4 butylidene on the aromatic polyester block), 2.46ppm(aromatic polyester block 1, hydrogen on the 3 propylidene structure intermediate sub methyl), the hydrogen on the 5.14ppm(PLA block methyne), the hydrogen on the 1.67ppm(PLA block methyl); Do not see the peak that all the other are produced by transesterify

¹³C-NMR: 170.0ppm (carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); 168.0ppm(the carbonyl carbon on the aromatic polyester block block), 133.2ppm(on the aromatic polyester block phenyl ring 1, carbon on 4), 129.3ppm(aromatic polyester block phenyl ring 2,3,5, carbon on 6), 65.4ppm(on the aromatic polyester block in the butylidene structure 1, carbon on 4 two methylene radical), 63.0ppm(in aromatic polyester block 1, the 3 propylidene structure on 1,3 methylene radical carbon and the structural carbon of ethylidene), 26.8ppm(aromatic polyester block 1, the carbon of 2 methylene radical of 3 propylidene structures) carbon on 2,3 two methylene radical in the butylidene structure on the 24.6ppm(aromatic polyester block), do not see peaks that all the other are produced by transesterify.

DSC: T _m(240 ℃) are corresponding to PE ₈₀T ₁₀B ₁₀The T block is the poly-dl-lactide block owing to what generate, so do not see the melting peak of PLA.

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is poly terephthalic acid-ethylene glycol _-The segmented copolymer of propylene glycol-butanediol ester and poly(lactic acid), in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₂, (CH ₂) ₃(CH ₂) ₄, (CH wherein ₂) ₂, (CH ₂) ₃(CH ₂) ₄Mol ratio be 90:10:10, R ₃Be C ₅H ₁₁-, the B section is the poly-dl-lactide block.

Embodiment 10

Synthesizing of poly terephthalic acid hexylene glycol ester (PHT) and poly(lactic acid) (PLA) segmented copolymer.

Step (1). the ring-opening polymerization that phenylcarbinol causes ring-type poly terephthalic acid hexylene glycol ester makes one-ended hydroxy poly terephthalic acid hexylene glycol ester.

Under nitrogen protection, with 10g ring-type poly terephthalic acid hexylene glycol ester, 0.3g benzylated polyol and 0.0103 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}=1:1: mixed solvent, make that the concentration of ring-type poly terephthalic acid hexylene glycol ester is 1.0Kg/L, the concentration of benzylated polyol is 30g/L.Be reflected under 150 ℃ and carry out, finish (fignal center of GPC monitoring monomer-free) through reaction in 20 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PHT causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the one-ended hydroxy PHT and the 1g L-rac-Lactide of 1g step (1) gained then, add the 20ml tetrachloroethane with syringe again; make that the concentration of PHT is 50g/L; the concentration of rac-Lactide is 0.05Kg/L, is warmed up to 80 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.02g Sn (Oct) with syringe again ₂, 130 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 5 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). in step (2), add 40ml V in the crude product of gained _Chloroform/ V _{Trifluoracetic acid}The mixed solvent of=2:1 makes that crude product concentration is 50g/L, and with the sedimentation of 200ml methyl alcohol, filtering drying obtains final product, yield 94.8%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: because the content of aromatic copolyester block is bigger in the multipolymer, solvability in chloroform is not very desirable, so be solvent with the ortho chloro phenol earlier, being made into 10mg/mL, being diluted to 1 mg/mL with chloroform again, is that 10 mixed solvent is a moving phase with the volume ratio of chloroform and ortho chloro phenol, flow velocity 1.0ml/min, make standard specimen with PS, wherein collection of illustrative plates presents normal distribution, records M _n=18.9K, M _w=25.7K, PDI=1.36

¹H-NMR: 8.05ppm (PHT block benzene ring hydrogen), 4.41ppm(PHT in the block hexylidene 1, hydrogen on 6 two methylene radical), 1.7ppm(PHT in the block hexylidene 3, hydrogen on 4 two methylene radical), 2.05ppm(PHT block hexylidene 2, hydrogen on 5 two methylene radical), 4.67ppm(PHT the hydrogen on 3,4 two methylene radical in the 1.55ppm(PHT block hexylidene hydrogen on two methylene radical that link to each other with oxygen on the block)), 1.75ppm(PHT in the block hexylidene 2, hydrogen on 5 two methylene radical), the hydrogen on the 5.42ppm(PLA block methyne), the hydrogen on the 1.68ppm(PLA block methyl); The peak that no PHN and PLA transesterify produce obtains m by integral area _PHN: m _PLA=1:1

¹³C-NMR: 170.0ppm (carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); 168.4ppm(PHT the carbonyl on the block), 133.0ppm(PHT the phenyl ring 2,3 on the 129.5ppm(PHT block carbon that links to each other with carbonyl on the block phenyl ring),, 4, carbon on 5), the carbon on two methylene radical that are connected with oxygen on the 63.6ppm(PHT block hexylidene structure), in the 25.2ppm(PHT block hexylidene 2, carbon on 5 two methylene radical), 20.6 the carbon in the ppm(PHT block hexylidene on 3,4 two methylene radical), do not see the peak that the exchange of PHT block and poly-lactic acid ester produces.

DSC: T _m(155 ℃) corresponding to the PLA block, T _m(145 ℃) are corresponding to the PHT block.

Resulting among this embodiment is poly terephthalic acid hexylene glycol ester and polylactic-acid block copolymer, in general formula, and the R of A segment structure formula ₁For , R ₂Be CH ₂) ₆, R ₃For

, the B section is the Poly-L-lactic acid block.

Embodiment 11

Contain two kinds of not poly terephthalic acids of isomorphism type poly(lactic acid)-1,4-hexanaphthene dimethyl ester (PCT) and poly(lactic acid) (PLA) segmented copolymer synthetic.

Step (1). phenylcarbinol causes ring-type poly terephthalic acid-1, and 4-hexanaphthene dimethyl ester (CCT) ring-opening polymerization makes one-ended hydroxy poly terephthalic acid-1,4-hexanaphthene dimethyl ester.

Under nitrogen protection, with 10g ring-type poly terephthalic acid-1,4-hexanaphthene dimethyl ester, 0.1g benzylated polyol and 0.0101 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml orthodichlorobenzene of handling through anhydrous and oxygen-free with syringe, make ring-type poly terephthalic acid-1, the concentration of 4-hexanaphthene dimethyl ester is 1.0Kg/L, and the concentration of benzylated polyol is 10g/L.Be reflected under 120 ℃ and carry out, finish (fignal center of GPC monitoring monomer-free) through reaction in 60 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PCT causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the one-ended hydroxy PCT and the 1g D-rac-Lactide of 1g step (1) gained then, add the 20ml tetrachloroethane with syringe again; make that the concentration of PCT is 50g/L; the concentration of rac-Lactide is 0.05Kg/L, is warmed up to 80 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.02g Sn (Oct) with syringe again ₂, 130 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 5 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). in step (2), add 40ml V in the crude product of gained _Chloroform/ V _{Trifluoracetic acid}The mixed solvent of=2:1 makes that crude product concentration is 50g/L, with the sedimentation of 200ml methyl alcohol, filtering drying

Step (4) .100ml reaction flask is handled through anhydrous and oxygen-free equally; under nitrogen atmosphere, cool off, under protection of nitrogen gas, add resultant product of 1g step (3) and 1g D then; the L-rac-Lactide; add the 10ml orthodichlorobenzene with syringe again, make that the concentration of polylactic-acid block copolymer is 100g/L, the concentration of rac-Lactide is 0.1Kg/L; be warmed up to 80 ℃; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.003g SnBr with syringe again ₂, 140 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 5 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (5). add the 40ml chloroform in crude product, make that crude product concentration is 50g/L, with the sedimentation of 200ml methyl alcohol, filtering drying obtains final product, yield 98.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=31.1K, M _w=42.3K, PDI=1.36

¹H-NMR: 8.25ppm (PCT block benzene ring hydrogen), the 4.37 ppm(PCT blocks hydrogen on two methylene radical that links to each other with oxygen), the hydrogen on 1.68～2.18 ppm(PCT block hexanaphthenes); 5.42ppm(PLA the hydrogen on the 1.68ppm(PLA block methyl hydrogen on the block methyne)); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _PCT: m _PLA=1:30

¹³C-NMR: 170.5ppm (carbonyl carbon on the PLA block), the methine carbon on the 69.3ppm(PLA block), the carbon on the 15.8ppm(PLA block methyl); 168.9ppm(PCT the carbonyl on the block), 134.4ppm(PCT the carbon that links to each other with carbonyl on the block phenyl ring), 130.5ppm(PCT the phenyl ring 2 on the block, carbon on 3,4,5), 73.1ppm(PCT the carbon on two methylene radical that are connected with oxygen on the block), 29.1ppm(PCT the carbon on the block methyne), mesomethylene carbon in the 35.0ppm(PCT block cyclohexyl), do not see the peak that the exchange of PCT block and poly-lactic acid ester produces.

DSC: T _m(175 ℃) are corresponding to the PLA block, because content very little, is not seen PCT block fusing point.

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

So what this embodiment obtained is poly terephthalic acid-1, the segmented copolymer of 4-hexanaphthene dimethyl ester and poly(lactic acid), in general formula, the R of A segment structure formula ₁For

, R ₂For

, R ₃For

, the B section is made up of two kinds of poly(lactic acid) blocks, is expressed as B ₂-B ₁-, B wherein ₁Be dextrorotation poly(lactic acid) block, B ₂Be the poly-dl-lactide block

Embodiment 12

The polyethylene glycol 2 (PEN) that contains two kinds of configuration poly(lactic acid) is synthetic with the segmented copolymer of poly(lactic acid) (PLA).

Step (1). the ring-opening polymerization of phenylcarbinol initiation ring-type polyethylene glycol 2 (CEN) makes one-ended hydroxy and gathers 2,6-naphthalic acid-glycol ester.

Under nitrogen protection, with 10gCEN, 0.2g cyclopentanol and 0.0102 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml tetrachloroethane of handling through anhydrous and oxygen-free with syringe, make that the concentration of CEN is 1.0Kg/L, the concentration of cyclopentanol is 20g/L.Be reflected under 180 ℃ and carry out, finish (fignal center of GPC monitoring monomer-free) through reaction in 3 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). the PEN of one-ended hydroxy causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off, under protection of nitrogen gas, add the one-ended hydroxy PEN and the 3g D of 1g step (1) gained then; the L-rac-Lactide; add the 10ml tetrachloroethane with syringe again, make that the concentration of PEN is 100g/L, the concentration of rac-Lactide is 0.3Kg/L; 120 ℃ of dissolvings; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.0004g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 3 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 40ml trifluoracetic acid, make and use the sedimentation of 150ml methyl alcohol by crude product concentration 100g/L, filtering drying obtains product

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 1g L-rac-Lactide of 1g step (3) gained then, add 10ml toluene with syringe again; make that the concentration of product of step (3) gained is 100g/L; the concentration of rac-Lactide is 0.1Kg/L, is warmed up to 80 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.01g SnCl with syringe again ₄, 110 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 6 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 40ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 50g/L, with the sedimentation of 160ml methyl alcohol, filtering drying obtains final product, yield 95.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data:

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, and flow velocity 1.0ml/min records M _n=35.1K, M _w=53.71K, PDI=1.53

¹H-NMR: the hydrogen on the 8.85ppm(PEN block naphthalene nucleus on 1,5), on the 8.15ppm(PEN block naphthalene nucleus 3, hydrogen on 4,7,8), 4.8ppm(PEN the hydrogen on the inferior second of block), the hydrogen on the 5.15ppm(PLA block methyne), the hydrogen on the 1.63ppm(PLA block methyl); Do not see the peak that produces by PEN and PLA transesterify, obtain m by integral area _PEN: m _PLA=1:7.

¹³C-NMR: 168.0ppm (carbonyl carbon on the PEN block), 131.2 the ppm (naphthalene nucleus 1 on the PEN block, carbon on 5), the 132.5ppm (naphthalene nucleus 2 on the PEN block, carbon on 6), the 130.0 ppm (naphthalene nucleus 3 on the PEN block, carbon on 7), the 131.0 ppm (naphthalene nucleus 4 on the PEN block, carbon on 8), the carbon on two methylene radical in the 66.2ppm(PEN block ethylidene), (170.0ppm the carbonyl carbon on the PLA block), 69.2ppm(PLA the carbon on the 15.7ppm(PLA block methyl methine carbon on the block)); Do not see the peak that all the other are produced by transesterify

DSC: T _m(280 ℃) corresponding to the PEN block, T _m(160 ℃) are corresponding to the poly(lactic acid) block

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is the segmented copolymer of PEN and PLA, in general formula, and the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₂, R ₃Be ring-C ₅H ₉-, B is made up of two kinds of poly(lactic acid) blocks, is expressed as B ₂-B ₁-, B wherein ₁Be poly-dl-lactide block, B ₂Be the Poly-L-lactic acid block.

Embodiment 13

Contain the poly-2 of two kinds of configuration poly(lactic acid), the segmented copolymer of 6-naphthalic acid propylene glycol ester (PTN) and poly(lactic acid) (PLA) synthetic.

Step (1). phenylcarbinol causes ring-type and gathers 2, and 6-naphthalic acid propylene glycol ester (CTN) ring-opening polymerization makes one-ended hydroxy and gathers 2,6-naphthalic acid propylene glycol ester.

Under nitrogen protection, with 10g CTN, 1.0g cyclopentanol and 0.0011g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 5ml tetrachloroethane of handling through anhydrous and oxygen-free with syringe, make that the concentration of CTN is 2.0Kg/L, the concentration of cyclopentanol is 200g/L.Be reflected under 180 ℃ and carry out, finish (fignal center of GPC monitoring monomer-free) through reaction in 3 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PTN causes the rac-Lactide polymerization.The 50ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the one-ended hydroxy PTN and the 1gL-rac-Lactide of 0.06g step (1) gained then, add the 2ml tetrachloroethane with syringe; make that the concentration of PTN is 30g/L; the concentration of rac-Lactide is 0.5Kg/L, is warmed up to 120 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0106 g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 6 hours, stopped reaction, and cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, be dissolved in the 10ml chloroform, make that crude product concentration is 100 g/L, with the sedimentation of 40ml methyl alcohol, filtering drying obtains product

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 8g D-rac-Lactide of 1g step (2) gained then, add the 10ml tetrachloroethane with syringe again; make that the concentration of product of step (2) gained is 100g/L; the concentration of rac-Lactide is 0.8Kg/L, is warmed up to 50 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0009g Sn (Oct) with syringe again ₂, 110 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 6 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 90ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 100g/L, with the sedimentation of 360ml methyl alcohol, filtering drying obtains final product, yield 99.1%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC

Data

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=60.1K, M _w=87.0K, PDI=1.45

¹H-NMR: on the 8.65ppm(PTN block naphthalene nucleus 1, hydrogen on 5), 8.05ppm(PTN on the block naphthalene nucleus 3, hydrogen on 4,7,8), hydrogen 4.65ppm(PTN block links to each other with oxygen on the methylene radical), hydrogen 2.35ppm(PTN block links to each other with oxygen not on the methylene radical), the hydrogen on the 5.15ppm(PLA block methyne), the hydrogen on the 1.63ppm(PLA block methyl); Do not see all the other by the peak that transesterify produces, the mass ratio that is obtained PLA:PTN by integral area is 120:1

¹³C-NMR: 168.6ppm (carbonyl carbon on the PTN block), 131.6 the ppm (naphthalene nucleus 1 on the PTN block, carbon on 5), 132.5ppm (the naphthalene nucleus 2 on the PTN block, carbon on 6), 130.0 the ppm (naphthalene nucleus 3 on the PTN block, carbon on 7), 131.0 the ppm (naphthalene nucleus 4 on the PTN block, carbon on 8), 66.2ppm(PTN in the block propylidene 1, carbon on 3 two methylene radical), 27.2ppm(PTN the carbon on the block propylidene intermediate sub methyl), (170.0ppm the carbonyl carbon on the PLA block), 69.1ppm(PLA the carbon on the 15.8ppm(PLA block methyl methine carbon on the block)); Do not see the peak that all the other are produced by transesterify

DSC: T _mThe stereoscopic composite that (220 ℃) generate corresponding to the poly(lactic acid) block of two kinds of configurations, T _m(160 ℃) are corresponding to the PLA block, because PTN content very little, is not seen its fusing point

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and illustrates that what obtain is segmented copolymer

Resulting among this embodiment is contain two kinds of configuration poly(lactic acid) poly-2,6-naphthalic acid propylene glycol ester and polylactic-acid block copolymer, and in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₃, R ₃Be ring-C ₅H ₉-; B is made up of two kinds of poly(lactic acid) blocks, is expressed as B ₂-B ₁-, B wherein ₁Be Poly-L-lactic acid block, B ₂Be dextrorotation poly(lactic acid) block.

Embodiment 14

Contain the poly-2 of three kinds of configuration poly(lactic acid), the segmented copolymer of 6-naphthalic acid butanediol ester (PBN) and poly(lactic acid) synthetic.

Step (1). methyl alcohol causes ring-type and gathers 2, and the ring-opening polymerization of 6-naphthalic acid butanediol ester (CBN) makes one-ended hydroxy and gathers 2,6-naphthalic acid butanediol ester

Under nitrogen protection, with 10g CBN, 1.0g propargyl ethanol and 0.011 g SnCl ₄Put into the reaction flask roasting, that use the chilled 100ml of nitrogen protection that overdoes.Add the 5ml tetrachloroethane of handling through anhydrous and oxygen-free with syringe, make that the concentration of CBN is 2Kg/L, the concentration of propargyl ethanol is 200g/L.Be reflected under 180 ℃ and carry out, finish (fignal center of the no CBN of GPC monitoring) through reaction in 5 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the CBN monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). one-ended hydroxy PBN causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the one-ended hydroxy PTT and the 1gD-rac-Lactide of 0.06g step (1) gained then, add the 2ml orthodichlorobenzene with syringe again; make that the concentration of PBN is 30g/L; the concentration of rac-Lactide is 0.5Kg/L, is warmed up to 60 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0106g SnCl with syringe again ₂, 60 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 24 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, be dissolved in the 20ml chloroform, make that crude product concentration is 50 g/L, with the sedimentation of 60ml methyl alcohol, filtering drying

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 20g L-rac-Lactide of 1g step (3) gained then, add the 10ml trichloromethane with syringe again; make that the concentration of product of step (3) gained is 100g/L; the concentration of rac-Lactide is 2Kg/L, is warmed up to 50 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.21g SnCl with syringe again ₂, 50 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 24 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 210ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 100g/L, with the sedimentation of 630ml methyl alcohol, filtering drying

Step (6). the product of step (5) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, under protection of nitrogen gas, adds the product and the 1g D of 1g step (5) gained then, and the L-rac-Lactide adds 5ml V with syringe again _{Trichloromethane}: V _{Methylene dichloride}The mixed solvent of=1:1 makes that the concentration of product of step (5) gained is 200g/L, and the concentration of rac-Lactide is 0.2Kg/L, is warmed up to 30 ℃, and under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.004g Sn (Oct) with syringe again ₂, 80 ℃ of down reactions, with the GPC monitoring, the fignal center of rac-Lactide disappears after 20 hours, stopped reaction, filter after the cooling white crude product.

Step (7). the 20ml chloroform is joined the crude product of gained in (6) in the step, make that crude product concentration is 100g/L, with the sedimentation of 100ml methyl alcohol, filtering drying obtains final product, yield 91.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC

Data

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=54.9K, M _w=85.10K, PDI=1.55

¹H-NMR: on the 8.698ppm(PBN block naphthalene nucleus 1, hydrogen on 5), 8.05ppm(PBN on the block naphthalene nucleus 3, hydrogen on 4,7,8), hydrogen 4.68ppm(PBN block links to each other with oxygen on the methylene radical), hydrogen 2.11ppm(PBN block links to each other with oxygen not on the methylene radical), the hydrogen on the 5.18ppm(PLA block methyne), the hydrogen on the 1.65ppm(PLA block methyl); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _PBN: m _PLA=1:350

¹³C-NMR: 168.7ppm (carbonyl carbon on the PBN block), 131.6 the ppm (naphthalene nucleus 1 on the PBN block, carbon on 5), 132.5ppm (the naphthalene nucleus 2 on the PBN block, carbon on 6), 130.1 the ppm (naphthalene nucleus 3 on the PBN block, carbon on 7), 131.1 the ppm (naphthalene nucleus 4 on the PBN block, carbon on 8), 66.2ppm(PBN in the block butylidene 1, carbon on 4 two methylene radical), 27.2ppm(PBN the carbon on the block butylidene intermediate sub methyl), (170.1ppm the carbonyl carbon on the PLA block), 69.6ppm(PLA the carbon on the 15.9ppm(PLA block methyl methine carbon on the block)); Do not see the peak that all the other are produced by transesterify

DSC: T _m(173 ℃) corresponding to the PLA block, T _m(220 ℃) because the content of PBN very little, do not see PBN block fusing point corresponding to the stereoscopic composite of the poly(lactic acid) block generation of two kinds of configurations

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer

Resulting among this embodiment is contain three kinds of configuration poly(lactic acid) poly-2, the segmented copolymer of 6-naphthalic acid butanediol ester and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₄, R ₃For

; B is made up of three kinds of poly(lactic acid) blocks, is expressed as B ₃-B ₂-B ₁-, B wherein ₁Be dextrorotation poly(lactic acid) block, B ₂Be Poly-L-lactic acid block, B ₃Be the poly-dl-lactide block.

Embodiment 15

Contain the poly-1 of three kinds of configuration poly(lactic acid), the segmented copolymer of 4-naphthalic acid propylene glycol ester and poly(lactic acid) (PLA) synthetic.

Step (1). vinyl carbinol causes ring-type and gathers 1, and the ring-opening polymerization of 4-naphthalic acid propylene glycol ester makes the one-ended hydroxy polyethylene glycol 1.

Under nitrogen protection, the 10g ring-type is gathered 1,4-naphthalic acid propylene glycol ester, 0.3g allyl alcohol and 0.0103 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}: V _{Trichlorobenzene}The mixed solvent of=1:1:1 makes that the concentration of ring-type polyethylene glycol 1 is 1.0Kg/L, and the concentration of allyl alcohol is 30g/L.Be reflected under 130 ℃ and carry out, finish (fignal center of GPC monitoring monomer-free) through reaction in 30 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). one-ended hydroxy gathers 1, and 4-naphthalic acid propylene glycol ester causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, then under protection of nitrogen gas; add the 0.1g one-ended hydroxy and gather 1,4-naphthalic acid propylene glycol ester and 2g D, L-rac-Lactide; add 10ml1 with syringe again, 2, the 4-trichlorobenzene; make and gather 1, the concentration of 4-naphthalic acid propylene glycol ester is 10g/L, and the concentration of rac-Lactide is 0.2Kg/L; be warmed up to 130 ℃; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.003g SnCl with syringe again ₄, 150 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 2 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 40ml chloroform, make and use the sedimentation of 120ml methyl alcohol, filtering drying by crude product concentration 50g/L

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 20g L-rac-Lactide of 1g step (3) gained then, add the 10ml methylene dichloride with syringe again; make that the concentration of product of step (3) gained is 100g/L; the concentration of rac-Lactide is 2Kg/L, is warmed up to 30 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.21g SnCl with syringe again ₂, 30 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 24 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 210ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 100g/L, with the sedimentation of 840ml methyl alcohol, filtering drying

Step (6). the product of step (5) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, under protection of nitrogen gas, adds the product and the 1g D-rac-Lactide of 1g step (5) gained then, adds 5ml V with syringe again _{Trichloromethane}: V _{Tetracol phenixin}: V _{Tetracol phenixin}=1:1:1 makes that the concentration of product of step (5) gained is 200g/L, and the concentration of rac-Lactide is 0.2Kg/L, is warmed up to 30 ℃, and under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.004gSn (Oct) with syringe again ₂, 80 ℃ of down reactions, with the GPC monitoring, the fignal center of rac-Lactide disappears after 20 hours, stopped reaction, filter after the cooling white crude product.

Step (7). the 20ml chloroform is joined the crude product of gained in (6) in the step, make that crude product concentration is 100g/L, with the sedimentation of 100ml methyl alcohol, filtering drying obtains final product, yield 91.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC

Data:

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=83.8K, M _w=121.51K, PDI=1.45

¹H-NMR: on the 8.75ppm(naphthalene nucleus 2, hydrogen on 3), 8.05ppm(on the naphthalene nucleus 6, hydrogen on 7), 8.55ppm(the hydrogen on the naphthalene nucleus on 5,8) 4.70ppm(is poly-1, the hydrogen in the 4-naphthalic acid propylene glycol ester on two methylene radical), 5.1ppm(PLA the hydrogen on the 1.6ppm(PLA block methyl hydrogen on the block methyne)); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _{Gather 1,4-naphthalic acid propylene glycol ester}: m _PLA=1:35

¹³C-NMR: 168.6ppm (poly-1, carbonyl carbon on the 4-naphthalic acid propylene glycol ester block), 132.7 ppm (poly-1, naphthalene nucleus 1 on the 4-naphthalic acid propylene glycol ester block, carbon on 4), 126.9ppm (poly-1, naphthalene nucleus 2 on the 4-naphthalic acid propylene glycol ester block, carbon on 3), 131.4 ppm (poly-1, naphthalene nucleus 5 on the 4-naphthalic acid propylene glycol ester block, carbon on 8), (127.9ppm poly-1, the carbon on 6,7 of the naphthalene nucleus on the 4-naphthalic acid propylene glycol ester block), 135.1ppm (poly-1, naphthalene nucleus 9 on the 4-naphthalic acid propylene glycol ester block, carbon on 10), 26.7ppm(gather 1, the carbon on the 4-naphthalic acid propylene glycol ester block propyl group intermediate sub methyl), 66.7ppm(poly-1, the 4-naphthalic acid propylene glycol ester block propyl group carbon on the methylene radical that links to each other with oxygen), (170.2ppm the carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.8ppm(PLA block methyl); Do not see the peak that all the other are produced by transesterify.

DSC: T _m(185 ℃) corresponding to poly-1,4-naphthalic acid propylene glycol ester block, T _m(155 ℃) corresponding to the PLA block, T _mThe stereoscopic composite that (205 ℃) form corresponding to isomorphism type PLA not

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer

Resulting among this embodiment is contain three kinds of configuration poly(lactic acid) poly-1, the segmented copolymer of 4-naphthalic acid propylene glycol ester and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₃, R ₃For

B is made up of three kinds of poly(lactic acid) blocks, is expressed as B ₃-B ₂-B ₁-, B wherein ₁Be poly-dl-lactide block, B ₂Be the Poly-L-lactic acid block,, B ₃Be dextrorotation poly(lactic acid) block.

Embodiment 16

Contain the poly-1 of three kinds of configuration poly(lactic acid), 4-naphthalic acid-1,4-hexanaphthene dimethyl ester and poly(lactic acid) (PLA) segmented copolymer synthetic.

Step (1) .1-nonyl alcohol causes ring-type and gathers 1,4-naphthalic acid-1, and the ring-opening polymerization of 4-hexanaphthene dimethyl ester makes one-ended hydroxy and gathers 2,6-naphthalic acid-1,4-hexanaphthene dimethyl ester.

Under nitrogen protection, the 10g ring-type is gathered 1,4-naphthalic acid-1,4-hexanaphthene dimethyl ester, 0.1g1-nonyl alcohol and 0.0101 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}The mixed solvent of=1:1 makes ring-type gather 1,4-naphthalic acid-1, and the concentration of 4-hexanaphthene dimethyl ester is 1.0Kg/L, the concentration of 1 nonyl alcohol is 10g/L.Be reflected under 170 ℃ and carry out, finish (the monomeric fignal center of the GPC no ring-type of monitoring) through reaction in 10 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). one-ended hydroxy gathers 1,4-naphthalic acid-1,4-hexanaphthene dimethyl ester causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 2g D-rac-Lactide of 0.1g step (1) gained then, add 10ml oil of mirbane with syringe again; make that the concentration that adds step (1) products therefrom is 10g/L; the concentration of rac-Lactide is 0.2Kg/L, is warmed up to 100 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.003g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 3 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 40ml chloroform, make and use the sedimentation of 150ml methyl alcohol by crude product concentration 52g/L, filtering drying obtains product

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off, under protection of nitrogen gas, add the product and the 3gD of 1.5g step (3) gained then; the L-rac-Lactide; add the 5ml tetracol phenixin with syringe again, make that the concentration of product of step (3) gained is 300g/L, the concentration of rac-Lactide is 0.6Kg/L; be warmed up to 50 ℃; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.0045g SnCl with syringe again ₂, 110 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 14 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 45ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 100g/L, with the sedimentation of 150ml methyl alcohol, filtering drying

Step (6). the product of step (5) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 1g L-rac-Lactide of 1g step (5) gained then, add the 5ml tetrahydrofuran (THF) with syringe again; make that the concentration of product of step (5) gained is 200g/L; the concentration of rac-Lactide is 0.2Kg/L, is warmed up to 30 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0002g Sn (Oct) with syringe again ₂, 80 ℃ of down reactions, with the GPC monitoring, the fignal center of rac-Lactide disappears after 20 hours, stopped reaction, filter after the cooling white crude product.

Step (7). the 20ml chloroform is joined the crude product of gained in (6) in the step, make that crude product concentration is 100g/L, with the sedimentation of 100ml methyl alcohol, filtering drying obtains final product, yield 91.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC

Data:

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=65.4K, M _w=101.4K, PDI=1.55

¹H-NMR: on the 8.75ppm(naphthalene nucleus 2, hydrogen on 3), 8.05ppm(on the naphthalene nucleus 6, hydrogen on 7), 8.55ppm(on the naphthalene nucleus 5, hydrogen on 8), 4.4ppm(poly-1,4-naphthalic acid-1, in the 4-hexanaphthene dimethyl ester block with cyclohexylidene 1, hydrogen on 4 two continuous methylene radical), 1.3～2.2ppm(gathers 1,4-naphthalic acid-1, the hydrogen on the 4-hexanaphthene dimethyl ester block cyclohexylidene), 5.1ppm(PLA the hydrogen on the 1.6ppm(PLA block methyl hydrogen on the block methyne)); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _{Gather 1,4-naphthalic acid-1,4-hexanaphthene dimethyl ester}: m _PLA=1:65.

¹³C-NMR: 168.6.0ppm (poly-1,4-naphthalic acid-1, the carbonyl carbon of 4-hexanaphthene dimethyl ester), 132.7 ppm (naphthalene nucleus 1,4 on carbon), (126.9ppm the carbon on the naphthalene nucleus prosposition), 131.4 ppm (naphthalene nucleus 5, carbon on 8), (127.9ppm naphthalene nucleus 6,7 on carbon), (135.1ppm naphthalene nucleus 9,10 on carbon), 61.2ppm(poly-1,4-naphthalic acid-1, carbon in the 4-hexanaphthene dimethyl ester block cyclohexylidene on 1,4 two continuous methylene radical), 25.2 ppm(poly-1,4-naphthalic acid-1, carbon in the 4-hexanaphthene dimethyl ester section cyclohexylidene on 1,4 two methyne), 18.6 ppm(poly-1,4-naphthalic acid-1, in the 4-hexanaphthene dimethyl ester block cyclohexylidene 2,3,5, carbon on 6 four methylene radical), (170.0ppm the carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); Do not see the peak that all the other are produced by transesterify.

DSC: T _m(168 ℃) corresponding to the PLA block, T _mThe stereoscopic composite that (208 ℃) form corresponding to isomorphism type PLA not, since poly-1,4-naphthalic acid-1, and 4-hexanaphthene dimethyl ester block content is not seen its fusing point very little

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer

Resulting among this embodiment is to contain three kinds of not isomorphism type poly(lactic acid) poly-1,4-naphthalic acid-1, and the segmented copolymer of 4-hexanaphthene dimethyl ester and poly(lactic acid), in general formula, the R of A segment structure formula ₁For

, R ₂For

, R ₃For

B is made up of three kinds of poly(lactic acid) blocks, is expressed as B ₃-B ₂-B ₁-, B wherein ₁Be dextrorotation poly(lactic acid) block, B ₂Be poly-dl-lactide block, B ₃Be the Poly-L-lactic acid block.

Embodiment 17

Contain the poly-1 of three kinds of configuration poly(lactic acid), the segmented copolymer of 4-naphthalic acid butanediol ester and poly(lactic acid) (PLA) synthetic.

Step (1) .1-nonyl alcohol causes ring-type and gathers 1, and the ring-opening polymerization of 4-naphthalic acid butanediol ester makes one-ended hydroxy and gathers 1,4-naphthalic acid butanediol ester.

Under nitrogen protection, the 10g ring-type is gathered 1,4-naphthalic acid butanediol ester, 0.1g1-decyl alcohol and 0.0101 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}The mixed solvent of=1:1 makes ring-type gather 1, and the concentration of 4-naphthalic acid butanediol ester is 1.0Kg/L, and the concentration of 1-decanol is 10g/L.Be reflected under 160 ℃ and carry out, finish (the monomeric fignal center of the GPC no ring-type of monitoring) through reaction in 20 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). the one-ended hydroxy polyethylene glycol 1 causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, and under protection of nitrogen gas, the one-ended hydroxy that adds 1g step (1) gained gathers 1 then, and 4-naphthalic acid butanediol ester and 3g D-rac-Lactide add 20ml V with syringe again _{Tetrachloroethane}: V _{Orthodichlorobenzene}: V _{Oil of mirbane}The mixed solvent of=1:1:1 makes and gathers 1 that the concentration of 4-naphthalic acid butanediol ester is 50g/L, and the concentration of rac-Lactide is 0.15Kg/L, is warmed up to 120 ℃, and under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.02g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 5 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 20ml trifluoracetic acid, make and use the sedimentation of 100ml methyl alcohol, filtering drying by crude product concentration 200g/L

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off, under protection of nitrogen gas, add the product and the 10gD of 1g step (3) gained then; the L-rac-Lactide; add the 5ml tetrahydrofuran (THF) with syringe again, make that the concentration of product of step (3) gained is 200g/L, the concentration of rac-Lactide is 2.0Kg/L; be warmed up to 30 ℃; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.0011g SnCl with syringe again ₂, 80 ℃ of down reactions, with the GPC monitoring, the fignal center of rac-Lactide disappears after 20 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 110ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 100g/L, with the sedimentation of 400ml methyl alcohol, filtering drying

Step (6). the product of step (5) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 3gL-rac-Lactide of 1.5g step (5) gained then, add the 5ml tetracol phenixin with syringe again; make that the concentration of product of step (5) gained is 300g/L; the concentration of rac-Lactide is 0.6Kg/L, is warmed up to 50 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0045g SnCl with syringe again ₂, 110 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 14 hours, stopped reaction, filter after the cooling white crude product.

Step (7). the 90ml chloroform is joined the crude product of gained in (6) in the step, make that crude product concentration is 50g/L, with the sedimentation of 180ml methyl alcohol, filtering drying obtains final product, yield 95.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC

Data

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=161.4K, M _w=243.7K, PDI=1.51

¹H-NMR: on the 8.75ppm(naphthalene nucleus 2, hydrogen on 3), the hydrogen on 6,7 on the 8.05ppm(naphthalene nucleus), 8.55ppm(on the naphthalene nucleus 5, hydrogen on 8), 4.70ppm(is poly-1, the hydrogen on two methylene radical that link to each other with oxygen in the 4-naphthalic acid butanediol ester), 2.55 ppm(poly-1, hydrogen on two methylene radical does not link to each other with oxygen in the 4-naphthalic acid butanediol ester), the hydrogen on the 5.1ppm(PLA block methyne), the hydrogen on the 1.6ppm(PLA block methyl); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _{Gather 1,4-naphthalic acid butanediol ester}: m _PLA=1:40.

¹³C-NMR: 168.6.0ppm (poly-1, carbonyl carbon on the 4-naphthalic acid butanediol ester block), 132.7 ppm (naphthalene nucleus 1, carbon on 4), 126.9ppm (naphthalene nucleus 2, carbon on 3), 131.4 ppm (naphthalene nucleus 5, carbon on 8), 127.9ppm (naphthalene nucleus 6, carbon on 7), 135.1ppm (naphthalene nucleus 9, carbon on 10), 63.7ppm(poly-1, carbon on two methylene radical links to each other with oxygen in the 4-naphthalic acid butanediol ester block butylidene), 26.3 ppm(gathers 1, the carbon on two methylene radical that do not link to each other with oxygen in the 4-naphthalic acid butanediol ester block butylidene), 170.0ppm (carbonyl carbon on the PLA block), 69.2ppm(PLA the carbon on the 15.7ppm(PLA block methyl methine carbon on the block)); Do not see the peak that all the other are produced by transesterify.

DSC: T _m(158 ℃) corresponding to the melting peak of poly(lactic acid), owing to gather 1,4-naphthalic acid butanediol ester block content is less, does not see its melting peak.

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is to contain three kinds of not isomorphism type poly(lactic acid) poly-1, the segmented copolymer of 4-naphthalic acid butanediol ester and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₄, R ₃Be C ₁₀H ₂₁-; B is made up of three kinds of poly(lactic acid) blocks, is expressed as B ₃-B ₂-B ₁-, B wherein ₁Be dextrorotation poly(lactic acid) block, B ₂Be poly-dl-lactide block, B ₃Be the Poly-L-lactic acid block.

Embodiment 18

Contain three kinds of not isomorphism type poly(lactic acid) poly-1,4-naphthalic acid hexylene glycol ester and poly(lactic acid) (PLA) segmented copolymer synthetic.

Step (1) .1-nonyl alcohol causes ring-type and gathers 1, and the ring-opening polymerization of 4-naphthalic acid hexylene glycol ester makes one-ended hydroxy and gathers 1,4-naphthalic acid hexylene glycol ester.

Under nitrogen protection, the 10g ring-type is gathered 1,4-naphthalic acid hexylene glycol ester, 0.1g1-nonyl alcohol and 0.0101 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}The mixed solvent of=1:1 makes the reaction monomers ring-type gather 1, and the concentration of 4-naphthalic acid hexylene glycol ester is 1.0Kg/L, and the concentration of 1 nonyl alcohol is 10g/L.Be reflected under 160 ℃ and carry out, finish (the monomeric fignal center of the GPC no ring-type of monitoring) through reaction in 20 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). one-ended hydroxy gathers 1, and 4-naphthalic acid hexylene glycol ester causes the rac-Lactide polymerization.The 50ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; then under protection of nitrogen gas; the one-ended hydroxy poly-1 that adds 0.06g step (1) gained; 4-naphthalic acid hexylene glycol ester and 1gD-rac-Lactide; add the 2ml tetrachloroethane with syringe; make one-ended hydroxy gather 1; the concentration of 4-naphthalic acid hexylene glycol ester is 30g/L; the concentration of rac-Lactide is 0.5Kg/L, is warmed up to 120 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0106 g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 6 hours, stopped reaction, and cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, be dissolved in the 10ml chloroform, make that crude product concentration is 100 g/L, with the sedimentation of 40ml methyl alcohol, filtering drying obtains product,

Step (4) .100ml reaction flask is handled through anhydrous and oxygen-free equally, cools off under nitrogen atmosphere, under protection of nitrogen gas, adds resulting product of 1g step (3) and 1g D then, and the L-rac-Lactide adds 10ml V with syringe again _{Tetrachloroethane}: V _{Orthodichlorobenzene}V _{Tetracol phenixin}The mixed solvent of=1:1:1 makes that the resulting production concentration of step (3) is 100g/L, and the concentration of rac-Lactide is 0.1Kg/L, is warmed up to 140 ℃, and under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.003g SnBr with syringe again ₂, 140 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 5 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (5). add the 40ml chloroform in crude product, make that crude product concentration is 50g/L, with the sedimentation of 200ml methyl alcohol, filtering drying obtains product,

Step (6). the product of step (5) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free equally; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add resulting product of 3g step (5) and 1g L-rac-Lactide then, add the 10ml orthodichlorobenzene with syringe again; make that the concentration of polylactic-acid block copolymer is 300g/L; the concentration of rac-Lactide is 0.1Kg/L, is warmed up to 140 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.004g SnBr with syringe again ₂, 140 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 3 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (7). add the 80ml chloroform in the crude product of gained in step (6), make that crude product concentration is 50g/L, with the sedimentation of 260ml methyl alcohol, filtering drying obtains final product, yield 97.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=31.1K, M _w=45.1K, PDI=1.45

¹H-NMR: on the 8.75ppm(naphthalene nucleus 2, hydrogen on 3), 8.05ppm(on the naphthalene nucleus 6, hydrogen on 7), 8.55ppm(on the naphthalene nucleus 5, hydrogen on 8), 4.70ppm(poly-1, the hydrogen on two methylene radical that link to each other with oxygen in the 4-naphthalic acid hexylene glycol ester), 2.55 ppm(gather 1, in the 4-naphthalic acid hexylene glycol ester hexylidene structure 2, hydrogen on 5 last two methylene radical), 2.05 ppm(are poly-1, in the 4-naphthalic acid hexylene glycol ester hexylidene structure 3, hydrogen on 4 last two methylene radical) hydrogen on the 1.6ppm(PLA block methyl hydrogen on the 5.1ppm(PLA block methyne)); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _{Gather 1,4-naphthalic acid hexylene glycol ester}: m _PLA=1:40.

¹³C-NMR: 168.6.0ppm (poly-1, carbonyl carbon on the 4-naphthalic acid hexylene glycol ester block), 132.7 ppm (naphthalene nucleus 1, carbon on 4), 126.9ppm (naphthalene nucleus 2, carbon on 3), 131.4 ppm (naphthalene nucleus 5, carbon on 8), 127.9ppm (naphthalene nucleus 6, carbon on 7), (135.1ppm naphthalene nucleus 9,10 on carbon), 63.7ppm(poly-1, the carbon on two methylene radical that link to each other with oxygen in the 4-naphthalic acid hexylene glycol ester block hexylidene), 26.3 ppm(poly-1, carbon in the 4-naphthalic acid hexylene glycol ester block hexylidene on 2,5), 21.3 ppm(poly-1, in the 4-naphthalic acid hexylene glycol ester block hexylidene 3, carbon on 4) 170.0ppm (carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); Do not see the peak that all the other are produced by transesterify.

DSC: T _m(175 ℃) corresponding to the PLA block, T _m(215 ℃) corresponding to two kinds of stereoscopic composites of forming of isomorphism type PLA block not, because that content very little, is seen is poly-1, and 4-naphthalic acid hexylene glycol ester block fusing point

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

So this embodiment obtains is to contain three kinds of not isomorphism type poly(lactic acid) poly-1, the segmented copolymer of 4-naphthalic acid hexylene glycol ester and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₆, R ₃Be C ₉H ₁₉-; The B section is made up of three kinds of poly(lactic acid) blocks, is expressed as B ₃-B ₂-B ₁-, B wherein ₁Be dextrorotation poly(lactic acid) block, B ₂Be poly-dl-lactide block, B ₃Be the Poly-L-lactic acid block.

Embodiment 19

Contain the poly-1 of three kinds of configuration poly(lactic acid), the synthesizing of the segmented copolymer of 5-naphthalic acid hexylene glycol ester and poly(lactic acid).

Step (1) .2-propyl alcohol causes ring-type and gathers 1, and the ring-opening polymerization of 5-naphthalic acid hexylene glycol ester makes one-ended hydroxy and gathers 1,5-naphthalic acid hexylene glycol ester.

Under nitrogen protection, the 10g ring-type is gathered 1,5-naphthalic acid hexylene glycol ester, 0.1g2-propyl alcohol and 0.0101 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}The mixed solvent of=1:1 makes the reaction monomers ring-type gather 1, and the concentration of 5-naphthalic acid hexylene glycol ester is 1.0Kg/L, and the concentration of 2-propyl alcohol is 10g/L.Be reflected under 160 ℃ and carry out, finish (the monomeric fignal center of the GPC no ring-type of monitoring) through reaction in 20 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 60 ℃ of vacuum dryings.

Step (2). one-ended hydroxy poly-1,5-naphthalic acid hexylene glycol ester causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; then under protection of nitrogen gas; the one-ended hydroxy poly-1 that adds 1g step (1) gained; 5-naphthalic acid hexylene glycol ester and 3g D; the L-rac-Lactide; add the 10ml tetrachloroethane with syringe again; make one-ended hydroxy gather 1, the concentration of 5-naphthalic acid hexylene glycol ester is 100g/L, and the concentration of rac-Lactide is 0.3Kg/L; 120 ℃ of dissolvings; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.0004g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 3 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 40ml trifluoracetic acid, make and use the sedimentation of 150ml methyl alcohol, filtering drying by crude product concentration 100g/L

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, under protection of nitrogen gas, adds the product and the 1g L-rac-Lactide of 1g step (3) gained then, adds 10ml V with syringe again _{Tetrachloroethane}: V _{Orthodichlorobenzene}The mixed solvent of=1:1 makes that the concentration of product of step (3) gained is 100g/L, and the concentration of rac-Lactide is 0.1Kg/L, is warmed up to 80 ℃, and under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.01g SnCl with syringe again ₄, 110 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 6 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 40ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 50g/L, with the sedimentation of 160ml methyl alcohol, filtering drying

Step (6). the product of step (5) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 10g D-rac-Lactide of 1g step (5) gained then, add 5ml toluene with syringe again; make that the concentration of product of step (5) gained is 200g/L; the concentration of rac-Lactide is 2Kg/L, is warmed up to 80 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.11g SnCl with syringe again ₄, 110 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 5 hours, stopped reaction, filter after the cooling white crude product.

Step (7). the 40ml chloroform is joined the crude product of gained in the step (6), make that crude product concentration is 50g/L, with the sedimentation of 160ml methyl alcohol, filtering drying obtains final product, yield 94.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC

Data:

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, and flow velocity 1.0ml/min records M _n=56.1K, M _w=85.27K, PDI=1.52

¹H-NMR: on the 8.75ppm(naphthalene nucleus 4, hydrogen on 8), 8.05ppm(on the naphthalene nucleus 2,3,6, hydrogen on 7), 4.71ppm(is poly-1, the hydrogen on two methylene radical that link to each other with oxygen in the 5-naphthalic acid hexylene glycol ester), 2.45 ppm(poly-1, hydrogen in the 5-naphthalic acid hexylene glycol ester hexylidene structure on 2,5 last two methylene radical), 2.08 ppm(poly-1, in the 5-naphthalic acid hexylene glycol ester hexylidene structure 3, hydrogen on 4 last two methylene radical), the hydrogen on the 5.15ppm(PLA block methyne), the hydrogen on the 1.65ppm(PLA block methyl); Do not see that the peak that 5-naphthalic acid hexylene glycol ester and poly-lactic acid ester exchange produce obtains m by integral area by gathering 1 _{Gather 1,5-naphthalic acid hexylene glycol ester}: m _PLA=1:80

¹³C-NMR: 171.0ppm (poly-1, carbonyl carbon on the 5-naphthalic acid hexylene glycol ester block), 126.9 ppm (naphthalene nucleus 1, carbon on 5), 132.7 ppm (naphthalene nucleus 2, carbon on 6), 131.4 ppm (naphthalene nucleus 3, carbon on 7), 129.6 ppm (naphthalene nucleus 4, carbon on 8), 134.1ppm(naphthalene nucleus 9, carbon on 10), 66.7ppm(poly-1, carbon on two methylene radical links to each other with oxygen in the 5-naphthalic acid hexylene glycol ester block hexylidene), 25.3 ppm(poly-1, carbon in the 5-naphthalic acid hexylene glycol ester block hexylidene on 2,5), 21.7 ppm(poly-1, in the 5-naphthalic acid hexylene glycol ester block hexylidene 3, carbon on 4) 170.0ppm (carbonyl carbon on the PLA block), the methine carbon on the 69.2ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); Do not see by gathering 1, the peak that 5-naphthalic acid hexylene glycol ester and poly-lactic acid ester exchange produce.

DSC: T _m(175 ℃) corresponding to the PLA block, T _m(205 ℃) corresponding to two kinds of stereoscopic composites of forming of isomorphism type PLA block not, because that content very little, is seen is poly-1, and 5-naphthalic acid hexylene glycol ester block fusing point

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is to gather 1, the segmented copolymer of 5-naphthalic acid hexylene glycol ester and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₆, the B section is made up of three kinds of poly(lactic acid) blocks, is expressed as B ₃-B ₂-B ₁-, R ₃For ; B wherein ₁Be poly-dl-lactide block, B ₂Be Poly-L-lactic acid block, B ₃Be dextrorotation poly(lactic acid) block.

Embodiment 20

Contain the poly-1 of three kinds of configuration poly(lactic acid), the synthesizing of the segmented copolymer of 5-naphthalic acid butanediol ester and poly(lactic acid).

Step (1) .1-nonyl alcohol causes ring-type and gathers 1, and the ring-opening polymerization of 5-naphthalic acid butanediol ester makes one-ended hydroxy and gathers 1,5-naphthalic acid butanediol ester.

Under nitrogen protection, the 10g ring-type is gathered 1,5-naphthalic acid butanediol ester, 0.1g1-decyl alcohol and 0.0101 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Orthodichlorobenzene}The mixed solvent of=1:1 makes ring-type gather 1, and the concentration of 5-naphthalic acid butanediol ester is 1.0Kg/L, and the concentration of 1-decanol is 10g/L.Be reflected under 160 ℃ and carry out, finish (the monomeric fignal center of the GPC no ring-type of monitoring) through reaction in 20 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). one-ended hydroxy gathers 1, and 5-naphthalic acid butanediol ester causes the rac-Lactide polymerization.The 50ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; then under protection of nitrogen gas; the one-ended hydroxy poly-1 that adds 0.06g step (1) gained; 5-naphthalic acid butanediol ester and 1gL-rac-Lactide; add the 2ml tetrachloroethane with syringe; make one-ended hydroxy gather 1; the concentration of 5-naphthalic acid butanediol ester is 30g/L; the concentration of rac-Lactide is 0.5Kg/L, is warmed up to 120 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0106 g Sn (Oct) with syringe again ₂, 120 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 6 hours, stopped reaction, and cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, be dissolved in the 10ml chloroform, make that crude product concentration is 100 g/L, with the sedimentation of 40ml methyl alcohol, filtering drying

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 8g D-rac-Lactide of 1g step (3) gained then, add the 10ml tetrachloroethane with syringe again; make that the concentration of product of step (3) gained is 100g/L; the concentration of rac-Lactide is 0.8Kg/L, is warmed up to 50 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0009g Sn (Oct) with syringe again ₂, 110 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 6 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 100ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 90g/L, with the sedimentation of 360ml methyl alcohol, filtering drying

Step (6). the product of step (5) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off, under protection of nitrogen gas, add the product and the 1g D of 1g step (5) gained then; the L-rac-Lactide; add the 10ml tetrachloroethane with syringe again, make that the concentration of product of step (5) gained is 100g/L, the concentration of rac-Lactide is 0.1Kg/L; be warmed up to 50 ℃; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.0002g Sn (Oct) with syringe again ₂, 110 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 5 hours, stopped reaction, filter after the cooling white crude product.

Step (7). the 25ml chloroform is joined the crude product of gained in (6) in the step, make that crude product concentration is 80g/L, with the sedimentation of 120ml methyl alcohol, filtering drying obtains final product, yield 97.1%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=90.1K, M _w=129.7K, PDI=1.44

¹H-NMR: the hydrogen on the 8.75ppm(naphthalene nucleus on 4,8), on the 8.05ppm(naphthalene nucleus 2,3, hydrogen on 6,7), 4.65ppm(poly-1, hydrogen on two methylene radical links to each other with oxygen in the 5-naphthalic acid butanediol ester), 2.45 ppm(is poly-1, the hydrogen on two methylene radical on the prosposition in the 5-naphthalic acid butanediol ester hexylidene structure), 5.10ppm(PLA the hydrogen on the 1.62ppm(PLA block methyl hydrogen on the block methyne)); Do not see that all the other by the peak that transesterify produces, obtain PLA by integral area: gather 1, the mass ratio of 5-naphthalic acid butanediol ester is 200:1

¹³C-NMR: 171.1ppm (poly-1, carbonyl carbon on the 5-naphthalic acid butanediol ester block), 126.9 ppm (naphthalene nucleus 1, carbon on 5), 132.7 ppm (naphthalene nucleus 2, carbon on 6), 131.4 ppm (naphthalene nucleus 3, carbon on 7), 129.6 ppm (naphthalene nucleus 4, carbon on 8), 134.1ppm(naphthalene nucleus 9, carbon on 10), 66.7ppm(poly-1, carbon on two methylene radical links to each other with oxygen in the 5-naphthalic acid butanediol ester block butylidene), 25.3 ppm(poly-1, in the 5-naphthalic acid butanediol ester block butylidene 2, carbon on 3), (170.1ppm the carbonyl carbon on the PLA block), the methine carbon on the 69.1ppm(PLA block), the carbon on the 15.7ppm(PLA block methyl); Do not see the peak that all the other are produced by transesterify.

DSC: T _mThe stereoscopic composite that (220 ℃) generate corresponding to the poly(lactic acid) block of two kinds of configurations, T _m(160 ℃) corresponding to the PLA block, owing to gather 1,5-naphthalic acid butanediol ester content is not seen its fusing point very little

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and illustrates that what obtain is segmented copolymer

Resulting among this embodiment is contain three kinds of configuration poly(lactic acid) poly-1, the segmented copolymer of 5-naphthalic acid butanediol ester and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For

, R ₂Be (CH ₂) ₄, R ₃Be C ₁₀H ₂₁-; 3 two kinds of poly(lactic acid) blocks of B are formed, and are expressed as B ₃-B ₂-B ₁-, B wherein ₁Be Poly-L-lactic acid block, B ₂Be dextrorotation poly(lactic acid) block, B ₃Be the poly-dl-lactide block.

Embodiment 21

Contain the poly-1 of three kinds of configuration poly(lactic acid), the synthesizing of the segmented copolymer of 5-naphthalic acid propylene glycol ester and poly(lactic acid).

Step (1) .1-octanol causes ring-type and gathers 1, and the ring-opening polymerization of 5-naphthalic acid butanediol ester makes one-ended hydroxy and gathers 1,4-naphthalic acid butanediol ester.

Under nitrogen protection, the 10g ring-type is gathered 1,5-naphthalic acid propylene glycol ester, 0.1g1-octanol and 0.0101 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 10ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Oil of mirbane}The mixed solvent of=1:1 makes ring-type gather 1, and the concentration of 5-naphthalic acid propylene glycol ester is 1.0Kg/L, and the concentration of 1-octanol is 10g/L.Be reflected under 160 ℃ and carry out, finish (the monomeric fignal center of the GPC no ring-type of monitoring) through reaction in 20 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). the both-end hydroxyl gathers 1, and 5-naphthalic acid propylene glycol ester causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free, cools off under nitrogen atmosphere, then under protection of nitrogen gas; the one-ended hydroxy poly-1 that adds 0.06g step (1) gained; 5-naphthalic acid propylene glycol ester and 1gD-rac-Lactide add the 2ml orthodichlorobenzene with syringe again, make poly-1; the concentration of 5-naphthalic acid propylene glycol ester is 30g/L; the concentration of rac-Lactide is 0.5Kg/L, is warmed up to 60 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.0106g SnCl with syringe again ₂, 60 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 24 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, be dissolved in the 20ml chloroform, make that crude product concentration is 50 g/L, with the sedimentation of 60ml methyl alcohol, filtering drying

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 20g L-rac-Lactide of 1g step (3) gained then, add the 10ml trichloromethane with syringe again; make that the concentration of product of step (3) gained is 100g/L; the concentration of rac-Lactide is 2Kg/L, is warmed up to 50 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.21g SnCl with syringe again ₂, 50 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 24 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 210ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 100g/L, with the sedimentation of 630ml methyl alcohol, filtering drying

Step (6). the product of step (5) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off, under protection of nitrogen gas, add the product and the 1g D of 3g step (5) gained then; the L-rac-Lactide; add the 10ml trichloromethane with syringe again, make that the concentration of product of step (5) gained is 300g/L, the concentration of rac-Lactide is 0.1Kg/L; be warmed up to 50 ℃; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.04g SnCl with syringe again ₂, 50 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 24 hours, stopped reaction, filter after the cooling white crude product.

Step (7). the 50ml chloroform is joined the crude product of gained in (6) in the step, make that crude product concentration is 80g/L, with the sedimentation of 150ml methyl alcohol, filtering drying obtains final product, yield 96.2%, be GPC, ¹H-NMR, ¹³The various signs of C-NMR, DSC.

Data

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=63.9K, M _w=100.96K, PDI=1.58

¹H-NMR: on the 8.75ppm(naphthalene nucleus 4, hydrogen on 8), on the 8.05ppm(naphthalene nucleus 2,3,6, hydrogen on 7), 4.75ppm(is poly-1, the hydrogen on two methylene radical that link to each other with oxygen in the 5-naphthalic acid propylene glycol ester), 2.55 ppm(poly-1, hydrogen in the 5-naphthalic acid propylene glycol ester propylidene structure on 2 last two methylene radical), the hydrogen on the 5.10ppm(PLA block methyne), the hydrogen on the 1.62ppm(PLA block methyl); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _{1,5-naphthalic acid propylene glycol ester}: m _PLA=1:350

¹³C-NMR: 171.0ppm (poly-1, carbonyl carbon on the 5-naphthalic acid propylene glycol ester block), 126.8 ppm (naphthalene nucleus 1, carbon on 5), 132.8 ppm (naphthalene nucleus 2, carbon on 6), 131.4 ppm (naphthalene nucleus 3, carbon on 7), 129.6 ppm (naphthalene nucleus 4, carbon on 8), 134.1ppm(naphthalene nucleus 9, carbon on 10), 66.7ppm(poly-1, carbon on two methylene radical links to each other with oxygen in the 5-naphthalic acid propylene glycol ester block propylidene), 25.3 ppm(poly-1, carbon in the 5-naphthalic acid propylene glycol ester block propylidene on 2), (170.0ppm the carbonyl carbon on the PLA block), 69.2ppm(PLA the carbon on the 15.6ppm(PLA block methyl methine carbon on the block)); Do not see the peak that all the other are produced by transesterify.

DSC: T _m(173 ℃) corresponding to the PLA block, T _m(220 ℃) corresponding to the stereoscopic composite of the poly(lactic acid) block generation of two kinds of configurations, owing to gather 1, the content of 5-naphthalic acid propylene glycol ester is not seen and is gathered 1,5-naphthalic acid propylene glycol ester block fusing point very little.

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is contain three kinds of configuration poly(lactic acid) poly-1, the segmented copolymer of 5-naphthalic acid propylene glycol ester and poly(lactic acid), and in general formula, the R of A segment structure formula ₁For , R ₂Be (CH ₂) ₃R ₃Be C ₈H ₁₇-; B is made up of three kinds of poly(lactic acid) blocks, is expressed as B ₃-B ₂-B ₁-, B wherein ₁Be dextrorotation poly(lactic acid) block, B ₂Be Poly-L-lactic acid block, B ₃Be the poly-dl-lactide block.

Embodiment 22

Poly-1,5 naphthalic acid-1 that contains three kinds of configuration poly(lactic acid), the segmented copolymer segmented copolymer of 4-hexanaphthene dimethyl ester ester and poly(lactic acid).

Step (1) .1-hexanol causes poly-1,5 naphthalic acid-1 of ring-type, and the ring-opening polymerization of 4-hexanaphthene dimethyl ester ester makes one-ended hydroxy and gathers 1,4-naphthalic acid butanediol ester.

Under nitrogen protection, with poly-1,5 naphthalic acid-1 of 10g ring-type, 4-hexanaphthene dimethyl ester, 0.05g1-hexanol and 0.01 g Sn (Oct) ₂Put into roasting through overdoing, as to use the chilled 100ml of nitrogen protection reaction flask.Add the 5ml V that handles through anhydrous and oxygen-free with syringe _{Tetrachloroethane}: V _{Oil of mirbane}: V _{Orthodichlorobenzene}The mixed solvent of=1:1:1 makes ring-type gather 1,5 naphthalic acid-1, and the concentration of 4-hexanaphthene dimethyl ester is 2.0Kg/L, and the concentration of 1-hexanol is 10g/L.Be reflected under 165 ℃ and carry out, finish (the monomeric fignal center of the GPC no ring-type of monitoring) through reaction in 25 minutes, cold filtration with same chloroform washing reaction product through no water treatment, is washed the monomer of traces of unreacted off, 80 ℃ of vacuum dryings.

Step (2). one-ended hydroxy is gathered 1,5 naphthalic acid-1, and 4-hexanaphthene dimethyl ester ester causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; then under protection of nitrogen gas; poly-1,5 naphthalic acid-1 of one-ended hydroxy that adds 0.1g step (1) gained, 4-hexanaphthene dimethyl ester ester and 2g D; the L-rac-Lactide; add 10ml1 with syringe again, 2, the 4-trichlorobenzene; make poly-1; 5 naphthalic acids-1, the concentration of 4-hexanaphthene dimethyl ester ester is 10g/L, the concentration of rac-Lactide is 0.2Kg/L; be warmed up to 130 ℃; under this temperature, reaction solution is the solution state of homogeneous transparent, adds 0.0021g SnCl with syringe again ₄, 150 ℃ of reactions down, with the GPC monitoring, the fignal center of rac-Lactide disappears after 2 hours, stopped reaction, cooled and filtered obtains white crude product.

Step (3). get the crude product of step (2) gained, add the 40ml chloroform, make and use the sedimentation of 120ml methyl alcohol, filtering drying by crude product concentration 50g/L.

Step (4). the product of step (3) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 20g L-rac-Lactide of 1g step (3) gained then, add the 10ml methylene dichloride with syringe again; make that the concentration of product of step (3) gained is 100g/L; the concentration of rac-Lactide is 2Kg/L, is warmed up to 30 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.21g SnCl with syringe again ₂, 30 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 24 hours, stopped reaction, filter after the cooling white crude product.

Step (5). the 210ml chloroform is joined the crude product of gained in (4) in the step, make that crude product concentration is 100g/L, with the sedimentation of 840ml methyl alcohol, filtering drying.

Step (6). the product of step (5) gained causes the rac-Lactide polymerization.The 100ml reaction flask is handled through anhydrous and oxygen-free; under nitrogen atmosphere, cool off; under protection of nitrogen gas, add the product and the 1gD-rac-Lactide of 1g step (5) gained then, add the 10ml tetrachloromethane with syringe again; make that the concentration of product of step (5) gained is 100g/L; the concentration of rac-Lactide is 1Kg/L, is warmed up to 30 ℃, under this temperature; reaction solution is the solution state of homogeneous transparent, adds 0.02g SnCl with syringe again ₂, 30 ℃ of down reactions disappear with the fignal center of GPC monitoring rac-Lactide after 24 hours, stopped reaction, filter after the cooling white crude product.

Step (7). the 20ml chloroform is joined the crude product of gained in (6) in the step, make that crude product concentration is 100g/L, with the sedimentation of 100ml methyl alcohol, filtering drying obtains final product

Data

GPC: with chloroform is moving phase, and flow velocity 1.0ml/min makes standard specimen with PS, and wherein collection of illustrative plates presents normal distribution, records M _n=103.8K, M _w=150.51K, PDI=1.45

¹H-NMR: the hydrogen on the 8.77ppm(naphthalene nucleus on 4,8), on the 8.06ppm(naphthalene nucleus 2, hydrogen on 3,6,7), 4.55ppm(poly-1,5-naphthalic acid-1, in the 4-hexanaphthene dimethyl ester block with cyclohexylidene 1, hydrogen on 4 two continuous methylene radical), 1.3～2.2ppm(gathers 1,5-naphthalic acid-1, the hydrogen on the 4-hexanaphthene dimethyl ester block cyclohexylidene), 5.10ppm(PLA the hydrogen on the 1.62ppm(PLA block methyl hydrogen on the block methyne)); Do not see that all the other by the peak that transesterify produces, obtain m by integral area _{Gather 1,5-naphthalic acid-1,4-hexanaphthene dimethyl ester}: m _PLA=1:60

¹³C-NMR: 171.0ppm (poly-1,5-naphthalic acid-1, carbonyl carbon on the 4-hexanaphthene dimethyl ester block), 126.8 ppm (naphthalene nucleus 1, carbon on 5), 132.8 ppm (naphthalene nucleus 2,6 on carbon), 131.4 ppm (naphthalene nucleus 3,7 on carbon), 129.6 ppm (naphthalene nucleus 4, carbon on 8), 134.1ppm(naphthalene nucleus 9, carbon on 10), 61.2ppm(poly-1,5-naphthalic acid-1 is in the 4-hexanaphthene dimethyl ester block cyclohexylidene 1, carbon on 4 two continuous methylene radical), 25.2 ppm(is poly-1,5-naphthalic acid-1 is in the 4-hexanaphthene dimethyl ester section cyclohexylidene 1, carbon on 4 two methynes), 18.6 ppm(is poly-1,5-naphthalic acid-1 is in the 4-hexanaphthene dimethyl ester block cyclohexylidene 2,3, carbon on 5,6 four methylene radical), 170.0ppm (carbonyl carbon on the PLA block), 68.2ppm(PLA the carbon on the 15.85ppm(PLA block methyl methine carbon on the block)); Do not see the peak that all the other are produced by transesterify.

DSC: T _m(205 ℃) corresponding to poly-1,5-naphthalic acid-1, and 4-hexanaphthene dimethyl ester block, T _m(155 ℃) corresponding to the PLA block, T _mThe stereoscopic composite that (220 ℃) form corresponding to left-handed and dextral poly(lactic acid) block.

By gpc chromatogram is unimodal, and nuclear magnetic spectrum does not have the peak that transesterify produces, and can illustrate that what obtain is segmented copolymer.

Resulting among this embodiment is contain three kinds of configuration poly(lactic acid) poly-1,5-naphthalic acid-1, and the segmented copolymer of 4-hexanaphthene dimethyl ester and poly(lactic acid), in general formula, the R of A segment structure formula ₁For

, R ₂For

, R ₃Be C ₆H ₁₃-; B is made up of three kinds of poly(lactic acid) blocks, is expressed as B ₃-B ₂-B ₁-, B wherein ₁Be poly-dl-lactide block, B ₂Be Poly-L-lactic acid block, B ₃Be dextrorotation poly(lactic acid) block.

Claims (10)

1. a polylactic-acid block copolymer is characterized in that this polylactic-acid block copolymer is a di-block copolymer, is expressed as A- b-B, bThe expression block;

A is an one-ended hydroxy aromatic polyester block, and structural formula is:

R ₁For ,

,

,

In one or more;

R ₂Be (CH ₂) ₂, (CH ₂) ₃, (CH ₂) ₄, (CH ₂) ₆,

In one or more;

R ₃For alkyl, contain carbon-carbon double bond unsaturated substituting group, contain the unsaturated substituting group of carbon-carbon triple bond or contain the unsaturated substituting group of phenyl ring;

B is the poly(lactic acid) block, and its structural formula is:

A kind of process for polylactic acid block copolymer production is characterized in that this method may further comprise the steps:

Step (1). the preparation of one-ended hydroxy aromatic polyester: under nitrogen protection, ring-type aromatic polyester oligopolymer, monohydroxy-alcohol and pink salt catalyzer are dissolved in the first kind organic solvent of handling through anhydrous and oxygen-free, under 120～180 ℃ of conditions, react, adopt gel permeation chromatograph monitoring reaction process in the reaction process, stopped reaction after the fignal center of ring-type aromatic polyester oligopolymer disappears; After reaction is finished, be cooled to normal temperature, filter and obtain required one-ended hydroxy aromatic polyester;

Described ring-type aromatic polyester oligopolymer is the ring-type polyethylene terephthalate, the ring-type Poly(Trimethylene Terephthalate), the ring-type polybutylene terephthalate, ring-type poly terephthalic acid hexylene glycol ester, ring-type poly terephthalic acid-1,4-hexanaphthene dimethyl ester, ring-type poly-1, the 4-(ethylene naphthalate), ring-type poly-1,4-naphthalic acid propylene glycol ester, ring-type poly-1,4-naphthalic acid butanediol ester, ring-type poly-1,4-naphthalic acid hexylene glycol ester, ring-type poly-1,4-naphthalic acid-1,4-hexanaphthene dimethyl ester, ring-type poly-1, the 5-(ethylene naphthalate), ring-type poly-1,5-naphthalic acid propylene glycol ester, ring-type poly-1,5-naphthalic acid butanediol ester, ring-type poly-1,5-naphthalic acid hexylene glycol ester, ring-type poly-1,5-naphthalic acid-1,4-hexanaphthene dimethyl ester, ring-type poly-2, the 6-(ethylene naphthalate), ring-type poly-2,6-naphthalic acid propylene glycol ester, ring-type poly-2,6-naphthalic acid butanediol ester, ring-type poly-2,6-naphthalic acid hexylene glycol ester, ring-type poly-2,6-naphthalic acid-1, one or more in the 4-hexanaphthene dimethyl ester;

Step (2). with one-ended hydroxy aromatic polyester process vacuum drying, make its moisture content smaller or equal to 20ppm, one-ended hydroxy aromatic polyester after the oven dry and first kind rac-Lactide are dissolved in the first kind organic solvent of handling through anhydrous and oxygen-free under 60～130 ℃, add the pink salt catalyzer again, 60～150 ℃ of reactions down; Adopt gel permeation chromatograph monitoring reaction process in the reaction process, stopped reaction after the fignal center of first kind rac-Lactide disappears; Reaction is finished postcooling to normal temperature, filters to obtain first kind crude product;

Described first kind rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, the L-rac-Lactide;

Step (3). the first kind crude product of step (2) gained is dissolved in the second class organic solvent, and the methyl alcohol with 3～5 times of volumes of the second class organic solvent carries out sedimentation again, and filtering drying obtains first kind product;

Step (4). the first kind product and the second class rac-Lactide are dissolved in the 3rd class organic solvent of handling through anhydrous and oxygen-free, add the pink salt catalyzer again, 30～140 ℃ of reactions down, adopt gel permeation chromatograph monitoring reaction process in the reaction process, stopped reaction after the fignal center of the second class rac-Lactide disappears; Reaction is finished postcooling to normal temperature, filters to obtain the second class crude product;

The described second class rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, the L-rac-Lactide, and different with first kind rac-Lactide type;

Step (5). the second class crude product of step (4) gained is dissolved in the chloroform, makes that the concentration of the second class crude product is 50～100g/L, the methyl alcohol with 3～5 times of volumes of chloroform carries out sedimentation again, and filtering drying obtains the second class product;

Step (6). the second class product and the 3rd class rac-Lactide are dissolved in the 3rd class organic solvent of handling through anhydrous and oxygen-free, add the pink salt catalyzer again, 30～140 ℃ of reactions down, adopt gel permeation chromatograph monitoring reaction process in the reaction process, stopped reaction after the fignal center of the 3rd class rac-Lactide disappears; Reaction is finished postcooling to normal temperature, filters to obtain the 3rd class crude product;

Described the 3rd class rac-Lactide is L-rac-Lactide, D-rac-Lactide or D, the L-rac-Lactide, and different with the type of the first kind rac-Lactide and the second class rac-Lactide;

Step (7). the 3rd class crude product of step (6) gained is dissolved in the chloroform, makes that the concentration of the 3rd class crude product is 50～100g/L, use the methyl alcohol sedimentation of 3～5 times of volumes of chloroform again, filtering drying obtains the 3rd class product; The 3rd class product is the segmented copolymer that comprises three kinds of configuration poly(lactic acid).

2. a kind of polylactic-acid block copolymer as claimed in claim 1 is characterized in that: described poly(lactic acid) block is one or more in Poly-L-lactic acid block, dextrorotation poly(lactic acid) block, the poly-dl-lactide block.

3. a kind of process for polylactic acid block copolymer production as claimed in claim 2, it is characterized in that: the concentration of the ring-type aromatic polyester oligopolymer in the step (1) after the dissolving is 0.2～2Kg/L, the concentration of the monohydroxy-alcohol after the dissolving is smaller or equal to 200g/L, add catalyzer quality be 0.01～1% of reactant ring-type aromatic polyester oligopolymer and monohydroxy-alcohol total mass.

4. a kind of process for polylactic acid block copolymer production as claimed in claim 2, it is characterized in that: the concentration of the one-ended hydroxy aromatic polyester in the step (2) after the dissolving is smaller or equal to 100g/L, the concentration of first kind rac-Lactide is smaller or equal to 2Kg/L, add the pink salt catalyzer quality be 0.01～1% of one-ended hydroxy aromatic polyester and first kind rac-Lactide total mass.

5. a kind of process for polylactic acid block copolymer production as claimed in claim 2 is characterized in that: the first kind organic solvent described in step (1) and (2) is orthodichlorobenzene, tetrachloroethane, oil of mirbane, 1,2, one or more in the 4-trichlorobenzene.

6. a kind of process for polylactic acid block copolymer production as claimed in claim 2, it is characterized in that: the second class organic solvent described in the step (3) is a kind of in chloroform, the trifluoracetic acid or both mixtures, and the concentration of the first kind crude product after the dissolving is 50～200g/L.

7. a kind of process for polylactic acid block copolymer production as claimed in claim 2 is characterized in that: the 3rd class organic solvent described in step (4) and (6) is one or more in methylene dichloride, chloroform, tetracol phenixin, toluene, tetrahydrofuran (THF), orthodichlorobenzene, the tetrachloroethane.

8. a kind of process for polylactic acid block copolymer production as claimed in claim 2 is characterized in that:

The concentration of the first kind product in the step (4) after the dissolving is smaller or equal to 300g/L, and the concentration of the second class rac-Lactide is smaller or equal to 2Kg/L, add the pink salt catalyzer quality be 0.01～1% of the first kind product and the second class rac-Lactide total mass.

9. the concentration of the second class product after the dissolving is smaller or equal to 300g/L in the step (6), and the concentration of the 3rd class rac-Lactide is smaller or equal to 2Kg/L, add the pink salt catalyzer quality be 0.01～1% of the second class product and the 3rd class rac-Lactide total mass.

10. a kind of process for polylactic acid block copolymer production as claimed in claim 2 is characterized in that: the pink salt catalyzer described in step (1), (2), (4) and (6) is Sn (Oct) ₂, SnCl ₂, SnCl ₄, SnBr ₂In a kind of.