CN105367770B

CN105367770B - A kind of aliphatic-aromatic-polylactic-acid block copolymer

Info

Publication number: CN105367770B
Application number: CN201410440262.XA
Authority: CN
Inventors: 张宝; 边新超; 孙敬茹; 李杲; 陈学思
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2014-08-29
Filing date: 2014-08-29
Publication date: 2018-06-29
Anticipated expiration: 2034-08-29
Also published as: CN105367770A

Abstract

The present invention provides a kind of aliphatic aromatic polylactic-acid block copolymers to be made by following preparation method：A) aromatic binary carboxylic acid class compound, aliphatic dicarboxylic acid class compound, dibastic alcohol compound and monomer are reacted, obtains the hydroxy-end capped aliphatic aromatic copolyesters of molten state；The monomer includes multicomponent alcoholics compound, Polycarboxylic acids or polybasic carboxylic acid esters compound；B) the hydroxy-end capped aliphatic aromatic copolyesters of lactide and molten state is subjected to polymerisation, obtains aliphatic aromatic polylactic-acid block copolymer.There is aliphatic aromatic to be copolymerized ester structure, the aliphatic aromatic copolymerization ester structure is the branch of aliphatic aromatic polylactic-acid block copolymer, can improve the melt strength of aliphatic aromatic polylactic-acid block copolymer in the copolymer.In addition, the aliphatic aromatic polylactic-acid block copolymer has higher elongation at break.

Description

A kind of aliphatic-aromatic-polylactic-acid block copolymer

Technical field

The invention belongs to technical field of organic synthesis more particularly to a kind of aliphatic-aromatic-polylactic acid block copolymerizations Object.

Background technology

The commodity that develop into of plastics industry bring cheap, object U.S. packaging, but largely use non-renewable petroleum resources The problems such as plastic products of production also bring serious shortage of resources and environmental pollution to the mankind.Solve the problems, such as the best of this Approach is the new degradation material of research and development.In the degradation material developed and utilized by people at present, polylactic acid (PLA) With excellent biocompatibility, biodegradability, final catabolite is carbon dioxide and water, will not cause dirt to environment Dye, concerned degree are higher.But containing a large amount of ester bond in PLA, hydrophily is poor, reduces the life of polylactic acid and other materials Object compatibility；The product that various PLA films, sheet material, the fiber prepared obtains after the secondary operation such as thermoforming, spinning can be wide It is general to be applied to the fields such as agricultural, health care, daily necessities, but in process, melt strength relatively low PLA makes It easily causes in the forming processes such as Extrusion Coating, blowing, foaming film bubble unstable and is ruptured, and makes its application by larger limit System.

In order to improve the melt strength of polylactic acid, many researchers have carried out largely the modification of polylactic acid in recent years Research.In patent CN100532420C, using dissaving polymer polydactyl acid, improve the mechanical property of polylactic acid and break Elongation is split, reduces the brittleness of polylactic acid, but complex viscosity substantially reduces, also indicates that melt strength.

Invention content

In view of this, the purpose of the present invention is to provide a kind of aliphatic-aromatic-polylactic-acid block copolymers.This hair The melt strength of aliphatic-aromatic-polylactic-acid block copolymer of bright offer is higher.

The present invention provides a kind of aliphatic-aromatic-polylactic-acid block copolymers, are made by following preparation method：

A) by aromatic binary carboxylic acid class compound, aliphatic dicarboxylic acid class compound, dibastic alcohol compound and list Body carries out esterification and polycondensation reaction, obtains the hydroxy-end capped aliphatic-aromatic copolyester of molten state；

The monomer includes multicomponent alcoholics compound, Polycarboxylic acids or polybasic carboxylic acid esters compound；

B) the hydroxy-end capped aliphatic-aromatic copolyester of the obtained molten state of lactide and the step a) is carried out Polymerisation obtains aliphatic-aromatic-polylactic-acid block copolymer.

Preferably, the temperature of esterification is 150 DEG C~230 DEG C in the step a)；

The time of esterification is 1h~10h in the step a).

Preferably, the temperature of polycondensation reaction is 210 DEG C~290 DEG C in the step a)；

The time of polycondensation reaction is 0.5h~48h in the step a)；

The pressure of polycondensation reaction is 10Pa~2000Pa in the step a).

Preferably, the temperature of polymerisation is 110 DEG C~180 DEG C in the step b)；

The time of polymerisation is 3h~50h in the step b).

Preferably, in the step a) aromatic binary carboxylic acid class compound and aliphatic dicarboxylic acid class compound it is total The amount ratio of the amount of substance and the substance of the dibastic alcohol compound is 1:0.8~1:2；

The amount ratio of the substance of the aromatic binary carboxylic acid class compound and aliphatic dicarboxylic acid class compound is 10:90 ~90:10.

Preferably, the matter of lactide and the hydroxy-end capped aliphatic-aromatic copolyester of molten state in the step b) Amount is than being 1:9~9:1.

Preferably, the aliphatic dicarboxylic acid class compound includes the aliphatic dicarboxylic acid class compound of C2~C40 In it is one or more；

The dibastic alcohol compound includes one or more in the dibastic alcohol compound of C2~C40.

The present invention provides aliphatic-aromatic-polylactic-acid block copolymer, features described in a kind of above-mentioned technical proposal It is, the aliphatic-aromatic-polylactic-acid block copolymer has structure shown in Formulas I or Formula II：

Wherein, the p1=20~1400, n1=5~200, m1=5~200, x1=1~20, y1=1~20；

The p2=20~1400, n2=5~200, m2=5~200, x2=1~40；

The M₁And M₂Independently selected from alkylene or-R₃-O-R₄, the R₃And R₄Independently selected from alkylene；

The A₁And A₂Independently selected from alkylene；

The R₁The group after hydroxyl is removed for multicomponent alcoholics compound；

The R₂For Polycarboxylic acids except the group after decarboxylate or polybasic carboxylic acid esters compound remove ester group Group afterwards；

The D₁And D₂Independently selected from aromatic radical or-R₅-O-R₆, the R₅And R₆Independently selected from aromatic radical；

The E₁And E₂Independently selected from structure shown in formula 101：

In formula 101, numbers of the q1 for branch, q1=1~50；

The E₃With structure shown in formula 102：

In formula 102, numbers of the q2 for branch, q2=1~50.

Preferably, the p1=50~1200, n1=10~150, m1=10~150, x1=1~15, y1=1~15, Q1=2~20；

The p2=50~1200, n2=10~150, m2=10~150, x2=1~30, q2=2~20.

Preferably, the M₁And M₂Independently selected from the alkylene of C2~C40 or-R₃-O-R₄, the R₃And R₄Independently Alkylene selected from C2~C20；

The A₁、A₂、R₁And R₂Independently selected from the alkylene of C2~C40.

A kind of aliphatic-aromatic-polylactic-acid block copolymer provided by the invention is made by following preparation method：A) will Aromatic binary carboxylic acid class compound, aliphatic dicarboxylic acid class compound, dibastic alcohol compound and monomer be esterified anti- Should and polycondensation reaction, obtain the hydroxy-end capped aliphatic-aromatic copolyester of molten state；The monomer includes polyalcohols Close object, Polycarboxylic acids or polybasic carboxylic acid esters compound；B) molten state for obtaining lactide and the step a) Hydroxy-end capped aliphatic-aromatic copolyester carry out polymerisation, obtain aliphatic-aromatic-polylactic acid block copolymerization Object.There is aliphatic-aromatic copolyester structure, institute in aliphatic-aromatic-polylactic-acid block copolymer provided by the invention The branch that aliphatic-aromatic copolyester structure is aliphatic-aromatic-polylactic-acid block copolymer is stated, fat can be improved The melt strength of race-aromatic series-polylactic-acid block copolymer.In addition, aliphatic-aromatic-polylactic acid provided by the invention is embedding Section copolymer has higher elongation at break.The experimental results showed that：Aliphatic-aromatic-polylactic acid provided by the invention is embedding For section copolymer when frequency is 0.1, complex viscosity is 3000Pa.S~7500Pa.S；When frequency is 100, complex viscosity is 1300Pa.S~1600Pa.S；The elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is up to 580%.

Aliphatic-aromatic copolyester is made in the present invention first, then using aliphatic-aromatic copolyester for initiator and Lactide polymerisation is made aliphatic-aromatic-polylactic-acid block copolymer, without using antioxidant, cost in the method It is low, it is not susceptible to degrade and the side reactions such as change colour, conducive to industrialization.

Description of the drawings

Fig. 1 is the nuclear magnetic resonance spectroscopy of aliphatic-aromatic-polylactic-acid block copolymer that the embodiment of the present invention 1 obtains Figure；

Fig. 2 is the plural number of aliphatic-aromatic-polylactic-acid block copolymer that polylactic acid and the embodiment of the present invention 1 obtain The curve graph that viscosity changes with frequency；

Fig. 3 is the energy storage of aliphatic-aromatic-polylactic-acid block copolymer that polylactic acid and the embodiment of the present invention 1 obtain The curve graph that modulus changes with frequency；

Fig. 4 is the loss of aliphatic-aromatic-polylactic-acid block copolymer that polylactic acid and the embodiment of the present invention 1 obtain The curve graph that modulus changes with frequency；

The stress of aliphatic-aromatic-polylactic-acid block copolymer that Fig. 5 is obtained for polylactic acid and the embodiment of the present invention 3- Strain curve figure.

Specific embodiment

There is aliphatic-aromatic copolyester knot in aliphatic-aromatic-polylactic-acid block copolymer provided by the invention Structure, the aliphatic-aromatic copolyester structure are the branch of aliphatic-aromatic-polylactic-acid block copolymer, can be improved The melt strength of aliphatic-aromatic-polylactic-acid block copolymer.In addition, aliphatic-aromatic provided by the invention-poly- breast Sour block copolymer has higher elongation at break.The experimental results showed that：Aliphatic-aromatic provided by the invention-poly- breast For sour block copolymer when frequency is 0.1, complex viscosity is 3000Pa.S~7500Pa.S；When frequency is 100, complex viscosity is 1300Pa.S~1600Pa.S；The elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is up to 580%.

Aliphatic-aromatic copolyester is made in the present invention first, then using aliphatic-aromatic copolyester for initiator and Lactide carries out polymerisation, and aliphatic-aromatic-polylactic-acid block copolymer is made.Without using antioxidant in the method, It is at low cost, it is not susceptible to degrade and the side reactions such as change colour, conducive to industrialization.

The present invention is by aromatic binary carboxylic acid class compound, aliphatic dicarboxylic acid class compound, dibastic alcohol compound Esterification and polycondensation reaction are carried out with monomer, obtains the hydroxy-end capped aliphatic-aromatic copolyester of molten state；The list Body includes multicomponent alcoholics compound, Polycarboxylic acids or polybasic carboxylic acid esters compound.The present invention is anti-to the esterification It should be not particularly limited with the condition of polycondensation reaction, preferably carry out in the absence of oxygen, preferably pass through nitrogen or inert gas Realize the environment of anaerobic.The present invention does not have the inert gas special limitation, using well known to those skilled in the art lazy Property gas, preferably argon gas or helium.

The present invention is to the aromatic binary carboxylic acid class compound, aliphatic dicarboxylic acid class compound, di-alcohols The sequence for closing object and monomer mixing does not have special limitation, preferably by the aromatic binary carboxylic acid class compound and aliphatic two First carboxylic acid compound first mixes, then is mixed successively with the dibastic alcohol compound and monomer.

The present invention preferably in the presence of a catalyst, by the aromatic binary carboxylic acid class compound, binary aliphatic carboxylic Acid compounds, dibastic alcohol compound and monomer carry out esterification and polycondensation reaction.The present invention is in order to distinguish following technologies Catalyst in scheme, the catalyst that by esterification and polycondensation reaction when uses are named as the first catalyst.The present invention is to institute State aromatic binary carboxylic acid class compound, aliphatic dicarboxylic acid class compound, dibastic alcohol compound, monomer and the first catalysis The order by merging of agent does not have special limitation, preferably by the aromatic binary carboxylic acid class compound and aliphatic dicarboxylic acid class Compound first mixes, then is mixed successively with the dibastic alcohol compound, monomer and the first catalyst.In the present invention, it is described First catalyst preferably includes the change of the compound containing aluminium, the compound containing zinc, stanniferous compound, p-methyl benzenesulfonic acid and titaniferous Close object in it is one or more, more preferably including butyl titanate, stannous chloride, isopropyl titanate, stannous octoate, zinc acetate and It is one or more in p-methyl benzenesulfonic acid；The quality of first catalyst and the aliphatic dicarboxylic acid class compound and virtue The total mass ratio of fragrant race's dicarboxylic acids class compound is preferably 0.0001~0.01:1, more preferably 0.001~0.008:1, most Preferably 0.01~0.005:1.

In the present invention, the aromatic binary carboxylic acid class compound includes aromatic binary carboxylic acid and aromatic dicarboxylic carboxylic It is one or more in acid derivative；The aromatic binary carboxylic acid class compound preferably includes terephthalic acid (TPA), isophthalic two Formic acid, phthalic acid, phenylate dioctyl phthalate, benzophenone dicarboxylic acid, aromatic diacid acid anhydride, naphthalenedicarboxylic acid, aromatic diacid list alkane One or more in base ester and the double Arrcostabs of aromatic diacid, monoalkyl ester includes first in the aromatic diacid monoalkyl ester Ester, 2- ethylhexyls or butyl benzyl ester；Double Arrcostabs include dimethyl ester, two-ethyl in the double Arrcostabs of the aromatic diacid Ester, two-propyl diester, di-n-butyl ester, di-t-butyl ester or Di-Isobutyl ester；

The aromatic binary carboxylic acid class compound more preferably includes terephthalic acid (TPA), dimethyl terephthalate (DMT), naphthalene two Formic acid, naphthalene diformic acid dimethyl ester, biphenyl dicarboxylic acid, biphenyl dicarboxylic acid dimethyl ester and one kind or more in diethyl terephthalate Kind.

In the present invention, the aliphatic dicarboxylic acid class compound includes aliphatic dicarboxylic acid and binary aliphatic carboxylic One or more in acid derivative, aliphatic dicarboxylic acid class compound is excellent described in the aliphatic dicarboxylic acid analog derivative Choosing include it is one or more in the aliphatic dicarboxylic acid class compound of carbon atom number 2~40, most preferably including methyl fourth two Acid, 2,2- dimethyl succinic acids, adipic acid, succinic acid, succinic anhydride, C2~C40 aliphatic dicarboxylic acid monoalkyl ester and It is one or more in the double Arrcostabs of aliphatic acid dicarboxylic acids of C2~C40；Most preferably include adipic acid, succinic acid, succinic acid It is one or more in acid anhydride and dimethyl succinate.

In the present invention, the dibastic alcohol compound preferably includes one kind in the dibastic alcohol compound of C2~C40 Or it is a variety of, more preferably including ethylene glycol, propylene glycol, 1,2-PD, 1,4-butanediol, 1,3-BDO, 1,2- butanediols, 2, 3- butanediols, 1,5- pentanediols, bis- amylalcohols of 1,4-, 1,3- pentanediols, 1,2- pentanediols, 2,3- pentanediols, 2,4-PD, 2- Methyl -2,4-PD, 2,4- dimethyl -2,4-PD, 2,2,4- trimethyl -1,3- pentanediols, 1,6-HD, 1,5- Hexylene glycol, 1,4- hexylene glycols, 1,3- hexylene glycols, 1,2- hexylene glycols, 2,5-HD, 2- ethyl -1,3- hexylene glycols, 2,5- diformazans Base -2,5-HD, phenyl -1,2- ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, two contractings 3 third Glycol, 1,2- rings pentanediol, 1,3- rings pentanediol, 1,2- cyclohexanediols, 1,3- cyclohexanediols, 1,4- cyclohexanediols, 3- methoxies Base -1,2- propylene glycol, 1,7- heptandiols, 1,2- heptandiols, 1,8- ethohexadiols, 1,2- ethohexadiols, 1,9- nonanediols, the 1,10- last of the ten Heavenly stems Glycol, Decane-1,2-diol, 1,11- undecanes, 1,2- dodecanediols, 1,12- dodecanediols, 1,13- tridecanes two Alcohol, 1,14- tetradecane diols, 1,15- pentadecane diols, 1,16- hexadecane diols, 1,17- heptadecane diols, 1,18- 18 It is one or more in alkane glycol, 1,19- nonadecanes glycol and 1,20- icosane diols；Most preferably include 1,4- butanediols, 1, 3- butanediols, 1,2- butanediols, 2,3- butanediols, 1,6-HD, 1,5- hexylene glycols, 1,4- hexylene glycols, 1,3- hexylene glycols, 1, 2- hexylene glycols, 2,5-HD, Decane-1,2-diol, diethylene glycol, dipropylene glycol, 1,2- cyclohexanediols, 1,3- hexamethylenes two It is one or more in alcohol, 1,4- cyclohexanediols and polyethylene glycol.

In the present invention, the monomer includes multicomponent alcoholics compound, Polycarboxylic acids or polybasic carboxylic acid esters Compound；The monomer preferably includes glycerine, three polyglycereol, four polyglycereol, five polyglycereol, six polyglycereol, seven polyglycereol, eight poly- Glycerine, ten polyglycereol, 20 polyglycereol, pentaerythrite, bipentaerythrite, trimethylolethane, trimethylolpropane, oneself three Alcohol, butantriol, last of the ten Heavenly stems triol, penta triol, ring triol, triol in heptan, nonyl triol, pungent triol, L- Soviet Union butanol, erythrol, xylitol, Mannitol, sorbierite, maltitol, galactitol, inositol, trimesic acid, equal benzene tricarbonic acid's triethyl, equal benzene tricarboxylic Sour three isopropyl esters, tricarballylic acid, aconitic acid, butane tricarboxylic acid, cyclohexanetricarboxylic acid, hexamethylene tricarboxylic acids methyl esters, penta tricarboxylic Acid, ethane tricarboxylic acids, ethane tricarboxylic acids triethyl, tricarballylic acid's trimethyl, tricarballylic acid's triethyl, methane tricarboxylic acids three It is one or more in ethyl ester, butane tetracarboxylic acid, Pyromellitic Acid, biphenyltetracarboxyacid acid, ring butanetetra-carboxylic acid and hexamethylene hexacarboxylic acid, More preferably include glycerine, three polyglycereol, pentaerythrite, five polyglycereol, ten polyglycereol and one kind or more in butane tetracarboxylic acid Kind.In the present invention, the mass ratio of the monomer and dibastic alcohol compound is preferably 0.0005~0.2:1, more preferably 0.005~0.18:1, most preferably 0.05~0.1:1.

In the present invention, the total material of the aromatic binary carboxylic acid class compound and aliphatic dicarboxylic acid class compound Amount and the dibastic alcohol compound substance amount than preferably 1:0.8~2, more preferably 1:0.9~1.5；

The amount ratio of the substance of the aromatic binary carboxylic acid class compound and aliphatic dicarboxylic acid class compound is preferably 10:90~90:10, more preferably 20:80~80:20.

The present invention is preferably by the aromatic binary carboxylic acid class compound, aliphatic dicarboxylic acid class compound, dihydric alcohol When class compound and monomer carry out esterification, the water that esterification generates is collected, until when reaching theoretical water yield, then contract Poly- reaction.In the present invention, the temperature of the esterification is preferably 130 DEG C~230 DEG C, more preferably 140 DEG C~210 DEG C, Most preferably 160 DEG C~200 DEG C；The time of the esterification is preferably 1h~10h, more preferably 2h~8h, most preferably 4h~6h；The temperature of the polycondensation reaction is preferably 210 DEG C~290 DEG C, more preferably 230 DEG C~270 DEG C, most preferably 240 DEG C~260 DEG C；The time of the polycondensation reaction is preferably 0.5h~48h, more preferably 2h~40h, most preferably 5h~30h； The pressure of the polycondensation reaction is preferably 10Pa~2000Pa, more preferably 50Pa~1500Pa, and most preferably 150Pa~ 1000Pa。

The present invention carries out gel osmoticing chromatogram analysis to obtained aliphatic-aromatic copolyester, and test result shows：Institute The number-average molecular weight for stating aliphatic-aromatic copolyester is 10kg/mol~60kg/mol.

After obtaining the hydroxy-end capped aliphatic-aromatic copolyester of molten state, the present invention, will under anhydrous and oxygen-free environment Lactide and the hydroxy-end capped aliphatic-aromatic copolyester of the molten state carry out polymerisation, obtain aliphatic-fragrance Race-polylactic-acid block copolymer.In the present invention, the hydroxy-end capped aliphatic-aromatic copolyester conduct of the molten state While polymerisation raw material, also as the initiator of polymerisation.The present invention is to the hydroxyl of the lactide and the molten state The sequence of the aliphatic-aromatic copolyester mixing of base sealing end does not have special limitation, and the lactide preferably is added to institute State the hydroxy-end capped aliphatic-aromatic copolyester of molten state.The present invention preferably realizes anaerobic by nitrogen or inert gas Environment.

The present invention is in order to be conducive to the progress of polymerisation, preferably in the presence of the second catalyst, by the lactide and The hydroxy-end capped aliphatic-aromatic copolyester of the molten state carries out polymerisation.The present invention is to the lactide, second The sequence of the hydroxy-end capped aliphatic-aromatic copolyester mixing of catalyst and molten state does not have special limitation, preferably will The lactide is placed in the hydroxy-end capped aliphatic-aromatic copolyester of the molten state, then is added in second thereto and urged Agent.In the present invention, second catalyst preferably includes aluminium isopropoxide, divinyl zinc, stannous chloride and stannous octoate In it is one or more, more preferably include one or both of aluminium isopropoxide and stannous octoate；Second catalyst and third The mass ratio of lactide is preferably (0.01~1):100, more preferably (0.1~0.8):100, most preferably (0.3~0.6): 100。

Present invention preferably employs dry lactides；The water content of the lactide is preferably≤0.00035%.In the present invention In, the mass ratio of the hydroxy-end capped aliphatic-aromatic copolyester of the lactide and molten state is preferably 1:9~9:1, more Preferably 1:8~1:2, most preferably 1:7~1:3.

In the present invention, the temperature of the polymerisation is preferably 110 DEG C~180 DEG C, more preferably 120 DEG C~170 DEG C, Most preferably 130 DEG C~160 DEG C；The time of the polymerisation is preferably 3h~50h, more preferably 8h~40h, most preferably 12h~30h；

The present invention is preferably in the polymerization of the hydroxy-end capped aliphatic-aromatic copolyester and lactide of the molten condition After reaction, continue to heat up, vacuumize the unreacted lactide of removal, obtain the fat with structure shown in Formulas I or Formula II Race-aromatic series-polylactic-acid block copolymer.In the present invention, the pressure vacuumized is preferably 200Pa~1500Pa, more Preferably 250Pa~1000Pa；The temperature vacuumized is preferably 160 DEG C~185 DEG C, more preferably 175 DEG C~180 DEG C.

The number-average molecular weight of aliphatic-aromatic-polylactic-acid block copolymer that the present invention obtains for 30kg/mol~ 100kg/mol。

Present invention aliphatic-aromatic-polylactic-acid block copolymer according to above-mentioned technical proposal, preferably with Formulas I Or structure shown in Formula II：

Wherein, the p1=20~1400, n1=5~200, m1=5~200, x1=1~20, y1=1~20；

The p2=20~1400, n2=5~200, m2=5~200, x2=1~40；

The A₁And A₂Independently selected from alkylene；

The E₁And E₂Independently selected from structure shown in formula 101：

In formula 101, numbers of the q1 for branch, q1=1~50；

The E₃With structure shown in formula 102：

In formula 102, numbers of the q2 for branch, q2=1~50.

In the present invention, described p1, n1, m1, p2, n2 and m2 are the degree of polymerization；P1=20~1400, preferably p1= 50~1200, more preferable p1=100~1000；

P2=20~1400, preferably p2=50~1200, more preferable p2=100~1000；

N1=5~200, preferably n1=10~150, more preferable n1=20~130；

N2=5~200, preferably n2=10~150, more preferable n2=20~130；

M1=5~200, preferably m1=10~150, more preferable m1=20~130；

M2=5~200, preferably m2=10~150, more preferable m2=20~130；

Numbers of the q1 and q2 for branch, preferably q1=1~50, q1=2~20, more preferable q1=4~8；

Q2=1~50, preferably q1=2~20, more preferable q1=4~8.

In the present invention, the M₁And M₂Independently selected from alkylene or-R₃-O-R₄, the R₃And R₄Independently selected from Asia The alkylene or-R of alkyl, preferably C2~C40₃-O-R₄, the R₃And R₄Independently selected from the alkylene of C2~C20；More preferably For-(CH₂)₄-、-(CH₂)₂-O-(CH₂)₂-、-(CH₂)₃-O-(CH₂)₃-、- (CH₂)₂Or-(CH₂)₅₀-；

The A₁And A₂Independently selected from alkylene；It is preferred that the alkylene of C2~C40；More preferably-(CH₂)₄-、- (CH₂)₂-、-(CH₂)₈-、-(CH₂)₆-、-(CH₂)₅Or-(CH₂)₃₈-；

The R₁And R₂Independently selected from alkylene, preferably carbon atom number is 2~40 alkylene；More preferably

The D₁And D₂Independently selected from aromatic radical or-R₅-O-R₆, the R₅And R₆Independently selected from aromatic radical；The D₁ And D₂Independently preferablyOr

Specifically, it when terephthalic acid (TPA), adipic acid, butanediol and glycerine carry out esterification and polycondensation reaction, obtains The hydroxy-end capped aliphatic-aromatic copolyester of molten state with structure shown in formula III：

In formula III, the m3=5~200, n3=5~200, x3=1~20, y3=1~20；

By lactide and with the molten state of structure shown in formula III hydroxy-end capped aliphatic-aromatic copolyester into Row polymerisation obtains having aliphatic-aromatic-polylactic-acid block copolymer of structure shown in formula IV：

In formula IV, the p=20~1400, m=5~200, n=5~200, x=1~20, y=1~20, q=1.

Specifically, it when terephthalic acid (TPA), adipic acid, butanediol and the third three acid carry out esterification and polycondensation reaction, obtains The hydroxy-end capped aliphatic-aromatic copolyester of molten state with structure shown in Formula V：

In Formula V, the m4=5~200, n4=5~200, x4=1~20；

Lactide and the hydroxy-end capped aliphatic-aromatic copolyester with the molten state of structure shown in Formula V are carried out Polymerisation obtains having aliphatic-aromatic-polylactic-acid block copolymer of structure shown in Formula IV：

In the Formula IV, p5=20~1400, m5=5~200, n5=5~200, x5=1~20.

The present invention carries out obtained aliphatic-aromatic-polylactic-acid block copolymer the test of melt strength, specific mistake Journey is as follows：

By thickness for 1mm, diameter 25mm aliphatic-aromatic-block copolymer sample be placed in rotational rheometer into Row melt strength is tested, and dynamic frequency scanning is 5% in strain, and dynamic frequency is scanned from 0.1rad/s to 100rad/s, record Complex viscosity (η *) is with the variation of frequency.

Test result shows：Aliphatic-aromatic-polylactic-acid block copolymer provided by the invention frequency be 0.1 when, Complex viscosity is 3000Pa.S~7500Pa.S；When frequency is 100, complex viscosity is 1300Pa.S~1600Pa.S.

The present invention carries out tensile property test to aliphatic-aromatic-polylactic-acid block copolymer, and detailed process is as follows：

Aliphatic-aromatic-polylactic-acid block copolymer of 70mm × 4mm × 1mm is placed on tensile testing machine and is carried out Tensile property is tested, rate of extension 5mm/min, and test temperature is 23 DEG C, and aliphatic-aromatic-polylactic acid block is total to The elongation at break of polymers is recorded.

Test result shows：The elongation at break of aliphatic-aromatic-polylactic-acid block copolymer provided by the invention is most Up to 580%.

In order to further illustrate the present invention, with reference to embodiment to a kind of aliphatic-aromatic provided by the invention-poly- Lactic acid block copolymer is described in detail, but cannot they be interpreted as limiting the scope of the present invention.

Comparative example

The present invention carries out commercial goods PLA the test of complex viscosity, and test result shows：PLA frequency be 0.1 when, Complex viscosity is 2200Pa.S；

PLA is when frequency is 100, complex viscosity 1000Pa.S.

Embodiment 1

83g terephthalic acid (TPA)s, 73g adipic acids, 90g butanediols, 0.09g glycerine and 0.1g butyl titanates are placed in instead It answers in bottle, is warming up to 150 DEG C under normal pressure, carry out esterification, distillate moisture content, after 6h, when reaching theoretical water yield 36mL, rise To 210 DEG C, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges after 15h temperature, obtains poly- to benzene Dioctyl phthalate tetramethylene adipate；

The number average mol weight of the poly terephthalic acid tetramethylene adipate is 20.0kg/mol；

Above-mentioned poly terephthalic acid tetramethylene adipate 50g is taken, adds in the lactide and 0.2g of 200g dryings thereto Stannous octoate reacts 12h at 120 DEG C, is warming up to 180 DEG C and vacuumizes the unreacted monomer of removal, obtains aliphatic-fragrance Race-polylactic-acid block copolymer.

The present invention carries out hydrogen nuclear magnetic resonance spectrogram analysis to obtained aliphatic-aromatic-polylactic-acid block copolymer, such as Shown in Fig. 1, Fig. 1 is the nuclear magnetic resonance spectroscopy of aliphatic-aromatic-polylactic-acid block copolymer that the embodiment of the present invention 1 obtains Figure；

The aliphatic-aromatic that the present invention obtains-polylactic-acid block copolymer carries out gel osmoticing chromatogram analysis, fat The number average mol weight of race-aromatic series-polylactic-acid block copolymer is 55.0kg/mol.

The present invention flows obtained aliphatic-aromatic-polylactic-acid block copolymer with structure shown in formula III Become performance test, obtain the curve of its complex viscosity, storage modulus and loss modulus and frequency, as shown in Figure 2, Figure 3 and Figure 4, Fig. 2 is the complex viscosity of aliphatic-aromatic-polylactic-acid block copolymer that polylactic acid and the embodiment of the present invention 1 obtain with frequency The curve graph of rate variation, the curve that wherein curve 1 changes for the complex viscosity of polylactic acid with frequency, curve 2 are implemented for the present invention The curve that the complex viscosity of aliphatic-aromatic-polylactic-acid block copolymer that example 1 obtains changes with frequency；Fig. 3 is polylactic acid The curve that the storage modulus of aliphatic-aromatic-polylactic-acid block copolymer obtained with the embodiment of the present invention 1 changes with frequency Figure, wherein, the curve that curve 1 changes for the storage modulus of polylactic acid with frequency, curve 2 is the fat that the embodiment of the present invention 1 obtains The curve that the storage modulus of fat race-aromatic series-polylactic-acid block copolymer changes with frequency；Fig. 4 is real for polylactic acid and the present invention The curve graph that the loss modulus of aliphatic-aromatic-polylactic-acid block copolymer that example 1 obtains changes with frequency is applied, wherein, it is bent The curve that line 1 changes for the loss modulus of polylactic acid with frequency, curve 2 are aliphatic-fragrance that the embodiment of the present invention 1 obtains The curve that the loss modulus of race-polylactic-acid block copolymer changes with frequency.The system of the present invention it can be seen from Fig. 2, Fig. 3 and Fig. 4 The standby obtained complex viscosity of polylactic-acid block copolymer, storage modulus and loss modulus degree have larger compared with polylactic acid Raising.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The elongation at break of obtained polylactic-acid block copolymer is 150%.

The present invention carries out rheology testing, test result to obtained aliphatic-aromatic-polylactic-acid block copolymer Show：Aliphatic-aromatic-polylactic-acid block copolymer that the embodiment of the present invention 1 obtains is when frequency is 0.1, complex viscosity For 3500Pa.S, when frequency is 100, complex viscosity 1400Pa.S；Aliphatic-aromatic-polylactic-acid block copolymer is answered The curve of number viscosity and frequency is on PLA.

Embodiment 2

83g terephthalic acid (TPA)s, 73g adipic acids, 108g butanediols, 0.18g glycerine and 0.1g butyl titanates are placed in In reaction bulb, it is warming up to 160 DEG C under normal pressure, carries out esterification, distillate moisture content, after 4h, when reaching theoretical water yield 36mL, 290 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges after 1h, obtains poly- to benzene Dioctyl phthalate tetramethylene adipate, number average mol weight 21.0kg/mol；

Above-mentioned poly terephthalic acid tetramethylene adipate 50g is taken, adds in the lactide and 0.1g of 100g dryings thereto Stannous octoate reacts 5h at 180 DEG C, is warming up to 180 DEG C and vacuumizes the unreacted monomer of removal, it is embedding to obtain long-chain branch polylactic acid Section copolymer, number average mol weight 35.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：It is of the invention real It is 300% to apply the elongation at break of aliphatic-aromatic-block copolymer that example 2 obtains.

The present invention carries out rheology testing, test result to obtained aliphatic-aromatic-polylactic-acid block copolymer Show：When frequency is 0.1, complex viscosity is aliphatic-aromatic-polylactic-acid block copolymer that the embodiment of the present invention obtains 4000Pa.S, when frequency is 100, complex viscosity 1500Pa.S；Its complex viscosity and the curve of frequency pure PLA it On.

Embodiment 3

By 97g dimethyl terephthalate (DMT)s, 73g adipic acids, four fourth of 108g butanediols, 0.09g glycerine and 0.1g metatitanic acids Ester is placed in reaction bulb, is warming up to 230 DEG C under normal pressure, carries out esterification, distillates moisture content and methanol, after 3h, until reaching theoretical When water outlet and quantity of methyl alcohol 36mL, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, obtain after 5h To long chain branched polymers poly terephthalic acid tetramethylene adipate, number average mol weight 22.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid tetramethylene adipate 50g is taken, adds in the third dried friendships of 150g thereto Ester and 0.15g stannous octoates, react for 24 hours at 120 DEG C, are warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain fat Race-aromatic series-polylactic-acid block copolymer, number average mol weight 42.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, as shown in figure 5, Fig. 5 is polylactic acid The stress-strain curve of aliphatic-aromatic-polylactic-acid block copolymer obtained with the embodiment of the present invention 3, wherein, it is bent Line 1 is the load-deformation curve of polylactic acid；Curve 2 is aliphatic-aromatic-polylactic acid block that the embodiment of the present invention 3 obtains The load-deformation curve of copolymer.As seen from Figure 5, aliphatic-aromatic-polylactic acid block that the present embodiment obtains is total to The elongation at break of polymers is up to 370%, and compared with polylactic acid, elongation at break improves a lot.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 1 Examination, test result show：Aliphatic-aromatic-polylactic-acid block copolymer that the embodiment of the present invention 3 obtains is 0.1 in frequency When, complex viscosity 3400Pa.S, when frequency is 100, complex viscosity 1350Pa.S, complex viscosity is with frequency in PLA On.

Embodiment 4

By 97g dimethyl terephthalate (DMT)s, 73g adipic acids, four fourth of 108g butanediols, 0.18g glycerine and 0.1g metatitanic acids Ester is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carries out esterification, distillates moisture content, after 3h, until reach theoretical water outlet and During quantity of methyl alcohol 36mL, 220 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, goes out after 6h Material, obtains long chain branched polymers poly terephthalic acid tetramethylene adipate, number average mol weight 24.0kg/mol；

Take above-mentioned long-chain branch poly terephthalic acid tetramethylene adipate 50g, add in the dried lactides of 100g with 0.1g stannous octoates react 9h at 180 DEG C, vacuumize the unreacted monomer of removal, obtain aliphatic-aromatic-polylactic acid Block copolymer, number average mol weight 38.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 580%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 4 Examination obtains aliphatic-aromatic-polylactic-acid block copolymer when frequency is 0.1, complex viscosity 3900Pa.S, and frequency is When 100, complex viscosity 1450Pa.S；Its complex viscosity and the curve of frequency are on pure PLA.

Embodiment 5

83g terephthalic acid (TPA)s, 59g succinic acid, 90g butanediols, 0.09g glycerine and 0.1g zinc acetates are added into reaction bulb In, it is warming up to 160 DEG C under normal pressure, carries out esterification, distillate moisture content, after 3h, until when reaching theoretical water yield 36mL, be warming up to 230 DEG C, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges after 5h, obtain long chain branched polymers Poly terephthalic acid succinic acid-butanediol ester, number average mol weight 25.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid succinic acid-butanediol ester 50g is taken, adds in the lactide of 200g dryings thereto With 0.2g stannous octoates, react 50h at 110 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 56.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 125%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 5 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 3600Pa.S, when frequency is 100, complex viscosity 1500Pa.S.

Embodiment 6

83g terephthalic acid (TPA)s, 59g succinic acid, 108g butanediols, 0.18g glycerine and 0.1g stannous chlorides are added to instead It answers in bottle, is warming up to 160 DEG C under normal pressure, carry out esterification, distillate moisture content, after 5h, until when reaching theoretical water yield 36mL, rise To 220 DEG C, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges after 6h, obtain long-chain branch and gather temperature Close object poly terephthalic acid succinic acid-butanediol ester, number average mol weight 23.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid succinic acid-butanediol ester 50g is taken, adds in the third dried friendships of 100g thereto Ester and 0.2g stannous octoates, react 18h at 130 DEG C, are warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain fat Race-aromatic series-polylactic-acid block copolymer, number average mol weight 35.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 340%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 6 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 4200Pa.S, when frequency is 100, complex viscosity 1380Pa.S.

Embodiment 7

83g terephthalic acid (TPA)s, 73g adipic acids, 118g hexylene glycols, 0.09g glycerine and 0.1g butyl titanates are placed in In reaction bulb, it is warming up to 160 DEG C under normal pressure, carries out esterification, distillate moisture content, after 6h, until when reaching theoretical water yield 36mL, 260 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges after 2h, obtain long-chain branch Polymer poly terephthalic acid (TPA) adipic acid hexylene glycol ester, number average mol weight 25.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid adipic acid hexylene glycol ester 50g is taken, adds in the third dried friendships of 200g thereto Ester and 0.2g aluminium isopropoxides, react 48h at 110 DEG C, are warming up to 180 DEG C and vacuumize the unreacted monomer of removal, are drawn money on credit Chain polylactic-acid block copolymer, number average mol weight 47.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of long-chain branch polylactic-acid block copolymer is 133%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 7 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 3600Pa.S, when frequency is 100, complex viscosity 1350Pa.S.

Embodiment 8

83g terephthalic acid (TPA)s, 73g adipic acids, 118g hexylene glycols, 0.18g glycerine and 0.1g butyl titanates are placed in In reaction bulb, it is warming up to 160 DEG C under normal pressure, carries out esterification, distillate moisture content, after 6h, until reaching theoretical water outlet and quantity of methyl alcohol During 36mL, 220 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, obtain after 6h To poly terephthalic acid adipic acid hexylene glycol ester.Number average mol weight is 23.5kg/mol；

Above-mentioned long-chain branch poly terephthalic acid adipic acid hexylene glycol ester 50g is taken, adds in the lactide and 0.05g of 50g dryings Stannous chloride reacts 12h at 160 DEG C, is warming up to 180 DEG C and vacuumizes the unreacted monomer of removal, obtains aliphatic-fragrance Race-polylactic-acid block copolymer, number average mol weight 30.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 460%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 8 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 3950Pa.S, when frequency is 100, complex viscosity 1420Pa.S.

Embodiment 9

By 97g dimethyl terephthalate (DMT)s, 73g adipic acids, four fourth of 108g butanediols, 0.09g glycerine and 0.2g metatitanic acids Ester is placed in reaction bulb, is warming up to 140 DEG C under normal pressure, carries out esterification, distillates moisture content, after 10h, until reach theoretical water outlet and During quantity of methyl alcohol 36mL, 210 DEG C are then heated to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, It discharges after 18h, obtains long chain branched polymers poly terephthalic acid tetramethylene adipate, number average mol weight is 21.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid tetramethylene adipate 50g is taken, adds in the lactide and 0.2g of 200g dryings Stannous octoate reacts 36h at 120 DEG C, is warming up to 180 DEG C and vacuumizes the unreacted monomer of removal, obtains aliphatic-fragrance Race-polylactic-acid block copolymer, number average mol weight 50.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 139%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 9 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 3200Pa.S, when frequency is 100, complex viscosity 1300Pa.S.

Embodiment 10

By 97g dimethyl terephthalate (DMT)s, 73g adipic acids, 118g hexylene glycols, tri- polyglycereol of 0.36g and 0.2g metatitanic acids four Butyl ester is placed in reaction bulb, is warming up to 150 DEG C under normal pressure, carries out esterification, distillates moisture content, after 8h, until reaching theoretical water outlet During with quantity of methyl alcohol 36mL, it is warming up to 220 DEG C, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, after 6h Discharging, obtains long chain branched polymers poly terephthalic acid adipic acid hexylene glycol ester, number average mol weight 22.5kg/ mol；

Above-mentioned long-chain branch poly terephthalic acid tetramethylene adipate 50g is taken, adds in the lactide and 0.1g of 100g dryings Stannous octoate reacts 15h at 120 DEG C, is warming up to 180 DEG C and vacuumizes the unreacted monomer of removal, obtains aliphatic-fragrance Race-polylactic-acid block copolymer, number average mol weight 34.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 240%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 10 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 4100Pa.S, when frequency is 100, complex viscosity 1500Pa.S.

Embodiment 11

83g terephthalic acid (TPA)s, 73g adipic acids, 108g butanediols, 0.136g pentaerythrites and 0.2g butyl titanates are put In reaction bulb, it is warming up to 160 DEG C under normal pressure, carries out esterification, distillate moisture content, after 6h, until reaching theoretical water yield 36mL When, 230 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, grown after 4h Branched polymer poly terephthalic acid tetramethylene adipate, number average mol weight 23.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid tetramethylene adipate 50g is taken, adds in the lactide and 0.2g of 200g dryings Stannous octoate reacts 10h at 150 DEG C, is warming up to 180 DEG C and vacuumizes the unreacted monomer of removal, obtains aliphatic-fragrance Race-polylactic-acid block copolymer, number average mol weight 49.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 140%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 11 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 3800Pa.S, when frequency is 100, complex viscosity 1460Pa.S.

Embodiment 12

By 97g dimethyl terephthalate (DMT)s, 73g adipic acids, 118g hexylene glycols, 0.136g pentaerythrites and 0.2g metatitanic acids four Butyl ester is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carries out esterification, distillates moisture content, after 6h, until reaching theoretical water outlet During with quantity of methyl alcohol 36mL, it is warming up to 230 DEG C, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, after 5h Discharging, obtains long chain branched polymers poly terephthalic acid adipic acid hexylene glycol ester, number average mol weight 25.0kg/ mol；

Above-mentioned long-chain branch poly terephthalic acid tetramethylene adipate 50g is taken, adds in the lactide of 100g dryings thereto With 0.1g stannous octoates, react 25h at 120 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 33.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 245%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 12 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 3850Pa.S, when frequency is 100, complex viscosity 1500Pa.S.

Embodiment 13

83g terephthalic acid (TPA)s, 73g adipic acids, 90g butanediols, five polyglycereol of 0.45g and 0.1g butyl titanates are placed in In reaction bulb, it is warming up to 150 DEG C under normal pressure, carries out esterification, distillate moisture content, after 8h, until when reaching theoretical water yield 36mL, 220 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges after 8h, obtain long-chain branch Polymer poly terephthalic acid (TPA) tetramethylene adipate, number average mol weight 21.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid tetramethylene adipate 50g is taken, adds in the lactide of 200g dryings thereto With 0.2g stannous octoates, react 30h at 120 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 50.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 135%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 13 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity is 4100Pa S, when frequency is 100, complex viscosity 1480Pa.S.

Embodiment 14

103g naphthalenedicarboxylic acids, 73g adipic acids, 108g butanediols, five polyglycereol of 0.9g and 0.1g butyl titanates are placed in In reaction bulb, it is warming up to 230 DEG C under normal pressure, carries out esterification, distillate moisture content, after 5h, until when reaching theoretical water yield 36mL, 290 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges after 2h, obtain long-chain branch Poly- naphthalenedicarboxylic acid tetramethylene adipate, number average mol weight 22.5kg/mol；

The poly- naphthalenedicarboxylic acid tetramethylene adipate 50g of above-mentioned long-chain branch is taken, adds in the dried lactides of 200g thereto With 0.2g stannous octoates, react 12h at 170 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 51.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 130%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 14 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 4300Pa.S, when frequency is 100, complex viscosity 1520Pa.S.

Embodiment 15

By 120g naphthalene diformic acid dimethyl esters, 73g adipic acids, four fourth of 90g butanediols, five polyglycereol of 0.45g and 0.1g metatitanic acids Ester is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carries out esterification, distillates moisture content, after 10h, until reach theoretical water outlet and During quantity of methyl alcohol 36mL, 290 DEG C are then heated to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, 2h After discharge, obtain the poly- naphthalenedicarboxylic acid tetramethylene adipate of long-chain branch, number average mol weight 27.0kg/mol；

Take the poly- naphthalenedicarboxylic acid tetramethylene adipate 50g of above-mentioned long-chain branch, thereto add in 100g drying lactide with 0.1g stannous octoates react 20h at 160 DEG C, are warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic-virtue Fragrant race-polylactic-acid block copolymer, number average mol weight 39.0kg/mol.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 15 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 4200Pa.S, when frequency is 100, complex viscosity 1510Pa.S.

Embodiment 16

120g biphenyl dicarboxylic acids, 73g adipic acids, 118g hexylene glycols, five polyglycereol of 0.9g and 0.1g butyl titanates are put In reaction bulb, it is warming up to 160 DEG C under normal pressure, carries out esterification, distillate moisture content, after 12h, until reaching theoretical water yield 36mL When, 230 DEG C are then heated to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, obtain after 6h To the poly- biphenyl dicarboxylic acid adipic acid hexylene glycol ester of long-chain branch, number average mol weight 25.0kg/mol；

The poly- biphenyl dicarboxylic acid adipic acid hexylene glycol ester 50g of above-mentioned long-chain branch is taken, adds in the lactide of 200g dryings thereto With 0.2g stannous octoates, 15h is reacted at 180 DEG C, vacuumizes the unreacted monomer of removal, obtains aliphatic-aromatic-poly- breast Sour block copolymer, number average mol weight 49.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 120%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 16 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 4400Pa.S, when frequency is 100, complex viscosity 1540Pa.S.

Embodiment 17

By 135g biphenyl dicarboxylic acids dimethyl ester, 73g adipic acids, 118g hexylene glycols, five polyglycereol of 0.9g and 0.1g metatitanic acids four Butyl ester is placed in reaction bulb, is warming up to 220 DEG C under normal pressure, carries out esterification, after 12h, until reaching theoretical water outlet and quantity of methyl alcohol During 36mL, 260 DEG C are then heated to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, goes out after 2h Material, obtains the poly- biphenyl dicarboxylic acid adipic acid hexylene glycol ester of long-chain branch, and number average mol weight 23.0kg/mol is opposite Molecular weight distribution is 1.83；

The poly- biphenyl dicarboxylic acid adipic acid hexylene glycol ester 50g of above-mentioned long-chain branch is taken, adds in the lactide of 200g dryings thereto With 0.2g stannous octoates, reacted at 150 DEG C for 24 hours, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 47.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 137%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 17 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 4500Pa.S, when frequency is 100, complex viscosity 1570Pa.S.

Embodiment 18

83g terephthalic acid (TPA)s, 59g succinic acid, 108g butanediols, five polyglycereol of 0.9g and 0.1g butyl titanates are placed in In reaction bulb, it is warming up to 150 DEG C under normal pressure, carries out esterification, distillate moisture content, after 7h, until when reaching theoretical water yield 36mL, 230 DEG C are then heated to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, grown after 5h Branched polymer poly terephthalic acid succinic acid-butanediol ester, number average mol weight 24.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid succinic acid-butanediol ester 50g is taken, adds in the lactide of 100g dryings thereto With 0.1g stannous octoates, react 40h at 140 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 32.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 225%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 18 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 4700Pa.S, when frequency is 100, complex viscosity 1500Pa.S.

Embodiment 19

By 111g diethyl terephthalates, 73g adipic acids, 108 butanediols, 0.5g glycerine and 0.1g butyl titanates It is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carry out esterification, after 6h, until reaching theoretical water outlet and amount of alcohol 36mL When, 220 DEG C are then heated to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, obtain after 8h To long chain branched polymers poly terephthalic acid tetramethylene adipate, number average mol weight 25.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid tetramethylene adipate 50g is taken, adds in the lactide of 200g dryings thereto With 0.2g stannous octoates, react 36h at 130 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 48.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 132%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 19 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 6700Pa.S, when frequency is 100, complex viscosity 1600Pa.S.

Embodiment 20

By 111g diethyl terephthalates, 50g succinic anhydrides, 108g butanediols, tri- polyglycereol of 1.2g and 0.1g metatitanic acids Four butyl esters are placed in reaction bulb, are warming up to 160 DEG C under normal pressure, carry out esterification, after 5h, until reaching theoretical water outlet and amount of alcohol During 36mL, 215 DEG C are then heated to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, goes out after 18h Material, obtains long chain branched polymers poly terephthalic acid succinic acid-butanediol ester, number average mol weight 21.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid succinic acid-butanediol ester 50g is taken, adds in the lactide of 100g dryings thereto With 0.1g stannous octoates, react 15h at 120 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 37.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 241%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 20 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 7500Pa.S, when frequency is 100, complex viscosity 1600Pa.S.

Embodiment 21

By 111g diethyl terephthalates, 73g adipic acids, four fourth of 141g hexylene glycols, 0.09g glycerine and 0.1g metatitanic acids Ester is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carries out esterification, after 5h, until reaching theoretical water outlet and amount of alcohol 36mL When, 230 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, gathered after 8h Terephthalic acid (TPA) adipic acid hexylene glycol ester, number average mol weight 24.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid adipic acid hexylene glycol ester 50g is taken, adds in the lactide of 200g dryings thereto With 0.2g stannous octoates, react 16h at 160 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 50.0kg/mol.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 21 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 3600Pa.S, when frequency is 100, complex viscosity 1420Pa.S.

Embodiment 22

By 111g diethyl terephthalates, 73g dimethyl succinates, 200g polyethylene glycol-800s, 106g hexylene glycols, Tri- polyglycereol of 0.6g and 0.1g butyl titanates are placed in reaction bulb, and 150 DEG C are warming up under normal pressure, carry out esterification, after 8h, To when reaching theoretical water outlet and amount of alcohol 36mL, being warming up to 230 DEG C, decompression step by step to high vacuum state, pressure 700Pa, into Row polycondensation reaction discharges after 6h, obtains long chain branched polymers poly terephthalic acid succinic acid polyethylene glycol hexylene glycol ester, opposite Number average molecular weight is 25.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid succinic acid polyethylene glycol hexylene glycol ester 50g is taken, adds in 100g dryings thereto Lactide and 0.2g stannous octoates, reacted at 120 DEG C for 24 hours, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain To aliphatic-aromatic-polylactic-acid block copolymer, number average mol weight 35.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 250%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 22 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 5500Pa.S, when frequency is 100, complex viscosity 1520Pa.S.

Embodiment 23

By 111g diethyl terephthalates, 73g adipic acids, 180g decanediols, five polyglycereol of 0.9g and 0.1g metatitanic acids four Butyl ester is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carries out esterification, after 5h, until reaching theoretical water outlet and amount of alcohol During 36mL, 260 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, obtain after 2h To long chain branched polymers poly terephthalic acid adipic acid decanediol ester, number average mol weight 23.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid adipic acid decanediol ester 50g is taken, adds in the lactide of 200g dryings thereto With 0.2g stannous octoates, react 36h at 150 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 49.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 151%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 23 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 5700Pa.S, when frequency is 100, complex viscosity 1550Pa.S.

Embodiment 24

By 111g diethyl terephthalates, 73g adipic acids, 126g diethylene glycols, ten polyglycereol of 1.2g and 0.1g metatitanic acids Four butyl esters are placed in reaction bulb, are warming up to 160 DEG C under normal pressure, carry out esterification, after 7h, until reaching theoretical water outlet and amount of alcohol During 36mL, 230 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, obtain after 5h To long chain branched polymers poly terephthalic acid adipic acid binaryglycol ester, number average mol weight 23.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid adipic acid binaryglycol ester 50g is taken, add in 100g dryings thereto third is handed over Ester and 0.1g stannous octoates, react for 24 hours at 160 DEG C, are warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain fat Race-aromatic series-polylactic-acid block copolymer, number average mol weight 32.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 260%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 24 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 5000Pa.S, when frequency is 100, complex viscosity 1460Pa.S.

Embodiment 25

By 111g diethyl terephthalates, 73g adipic acids, 150g dipropylene glycols, ten polyglycereol of 1.2g and 0.2g Butyl titanate is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carries out esterification, after 6h, until reaching theoretical water outlet and second During alcohol amount 36mL, 260 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, goes out after 2h Material, obtains long-chain branch poly terephthalic acid adipic acid dipropylene glycol ester, number average mol weight 25.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid adipic acid dipropylene glycol ester 50g is taken, add in 200g dryings thereto third is handed over Ester and 0.2g stannous octoates, react 42h at 150 DEG C, are warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain fat Race-aromatic series-polylactic-acid block copolymer, number average mol weight 49.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 122%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 25 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 5300Pa.S, when frequency is 100, complex viscosity 1480Pa.S.

Embodiment 26

By 83g terephthalic acid (TPA)s, 73g adipic acids, 150g 1,4- cyclohexanediols, ten polyglycereol of 1.2g and 0.2g metatitanic acids four Butyl ester is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carries out esterification, after 8h, until when reaching theoretical water yield 36mL, 220 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges after 7h, obtain long-chain branch Polymer poly terephthalic acid (TPA) adipic acid cyclohexanediol ester, number average mol weight 21.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid adipic acid cyclohexanediol ester 50g is taken, add in 100g dryings thereto third is handed over Ester and 0.1g stannous octoates, react 48h at 130 DEG C, are warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain fat Race-aromatic series-polylactic-acid block copolymer, number average mol weight 31.0kg/mol.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 26 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 4700Pa.S, when frequency is 100, complex viscosity 1410Pa.S.

Embodiment 27

By 97g dimethyl terephthalate (DMT)s, 73g adipic acids, four fourth of 108g butanediols, 2g butane tetracarboxylic acid and 0.2g metatitanic acids Ester is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carries out esterification, after 6h, until reaching theoretical water outlet and quantity of methyl alcohol 36mL When, 230 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, grown after 5h Branched polymer poly terephthalic acid tetramethylene adipate, number average mol weight 25.0kg/mol.

Above-mentioned long-chain branch poly terephthalic acid tetramethylene adipate 50g is taken, adds in the lactide of 200g dryings thereto With 0.2g stannous octoates, react 28h at 140 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, using gel osmoticing chromatogram analysis, measure its number average mol weight is the present invention 49.0kg/mol。

The present invention carries out nuclear magnetic resonance spectroscopy identification to aliphatic-aromatic obtained above-polylactic-acid block copolymer.

Nuclear magnetic resonance spectroscopy is identified and gel osmoticing chromatogram analysis synthesis shows：The fat that the embodiment of the present invention 27 obtains Race-aromatic series-polylactic-acid block copolymer has structure shown in Formula II.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 138%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 27 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 3400Pa.S, when frequency is 100, complex viscosity 1380Pa.S.

Embodiment 28

By 97g dimethyl terephthalate (DMT)s, 59g succinic acid, four fourth of 141g hexylene glycols, 1.2g tricarballylic acids and 0.1g metatitanic acids Ester is placed in reaction bulb, is warming up to 160 DEG C under normal pressure, carries out esterification, after 6h, until reaching theoretical water outlet and quantity of methyl alcohol 36mL When, 220 DEG C are warming up to, decompression step by step to high vacuum state, pressure 700Pa carries out polycondensation reaction, discharges, grown after 6h Branched polymer poly terephthalic acid succinic acid hexylene glycol ester, number average mol weight 22.0kg/mol；

Above-mentioned long-chain branch poly terephthalic acid succinic acid hexylene glycol ester 50g is taken, adds in the lactide of 200g dryings thereto With 0.2g stannous octoates, react 5h at 180 DEG C, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, obtain aliphatic- Aromatic series-polylactic-acid block copolymer, number average mol weight 51.0kg/mol.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 28 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 3800Pa.S, when frequency is 100, complex viscosity 1420Pa.S.

Embodiment 29

The reaction kettle of 29.1 band, four blow vent through vacuumizing filling with inert gas cooling repeatedly, then in the situation for being passed through nitrogen Under, 400g polyethylene glycol-800s, 100g succinic anhydrides and 1g stannous chlorides are added in, this system is dropped and is sealed, is put into and is preheated to In 120 DEG C of oil bath, stirring 5h obtains the polyethylene glycol succinate of both-end carboxy blocking；

29.2 by 97g dimethyl terephthalate (DMT)s, 50g succinic acid, 100g both-end carboxy blockings polyethylene glycol succinic acid Ester, 141g hexylene glycols, ten polyglycereol of 1.2g and 0.1g butyl titanates are placed in reaction bulb, and 160 DEG C are warming up under normal pressure, are carried out Esterification after 6h, until when reaching theoretical water outlet and quantity of methyl alcohol 36mL, is warming up to 215 DEG C, decompression step by step to high vacuum state, Pressure is 700Pa, carries out polycondensation reaction, discharges after 15h, obtain long-chain branch poly terephthalic acid succinic acid polyethylene glycol succinic acid Hexylene glycol ester, number average mol weight 22.0kg/mol.

Above-mentioned long-chain branch poly terephthalic acid succinic acid polyethylene glycol succinic acid hexylene glycol ester 50g is taken, is added in thereto Lactide and the 0.1g stannous octoates of 150g dryings, react 18h at 150 DEG C, and being warming up to 180 DEG C, to vacuumize removal unreacted Monomer obtains aliphatic-aromatic-polylactic-acid block copolymer, number average mol weight 40.0kg/mol.

The present invention tests the mechanical property of product according to above-mentioned technical proposal, and test result shows：The present embodiment The obtained elongation at break of aliphatic-aromatic-polylactic-acid block copolymer is 170%.

The present invention carries out rheological property survey to the aliphatic-aromatic-polylactic-acid block copolymer obtained in embodiment 29 Examination obtains the curve of its complex viscosity and frequency on pure PLA；Aliphatic-aromatic-polylactic-acid block copolymer exists When frequency is 0.1, complex viscosity 4100Pa.S, when frequency is 100, complex viscosity 1420Pa.S.

As seen from the above embodiment, a kind of aliphatic-aromatic-polylactic-acid block copolymer provided by the invention is by following Preparation method is made：A) by aromatic binary carboxylic acid class compound, aliphatic dicarboxylic acid class compound, dibastic alcohol compound Esterification and polycondensation reaction are carried out with monomer, obtains the hydroxy-end capped aliphatic-aromatic copolyester of molten state；The list Body includes multicomponent alcoholics compound, Polycarboxylic acids or polybasic carboxylic acid esters compound；B) by lactide and the step The hydroxy-end capped aliphatic-aromatic copolyester of rapid molten state a) obtained carries out polymerisation, obtains aliphatic-fragrance Race-polylactic-acid block copolymer.There is aliphatic-virtue in aliphatic-aromatic-polylactic-acid block copolymer provided by the invention Fragrant race is copolymerized ester structure, and the aliphatic-aromatic copolyester structure is aliphatic-aromatic-polylactic-acid block copolymer Branch can improve the melt strength of aliphatic-aromatic-polylactic-acid block copolymer.In addition, fat provided by the invention Race-aromatic series-polylactic-acid block copolymer has higher elongation at break.The experimental results showed that：Fat provided by the invention For race-aromatic series-polylactic-acid block copolymer when frequency is 0.1, complex viscosity is 3000Pa.S~7500Pa.S；Frequency is When 100, complex viscosity is 1300Pa.S~1600Pa.S；The elongation at break of aliphatic-aromatic-polylactic-acid block copolymer Up to 460%.

Aliphatic-aromatic copolyester is made, then with aliphatic-aromatic in preparation method provided by the invention first Aliphatic-aromatic-polylactic-acid block copolymer is made with lactide polymerisation for initiator in copolyesters, need not in the method It is at low cost using antioxidant, it is not susceptible to degrade and the side reactions such as change colour, conducive to industrialization.

The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims

1. a kind of aliphatic-aromatic-polylactic-acid block copolymer, is made by following preparation method：

A) by aromatic binary carboxylic acid class compound, aliphatic dicarboxylic acid class compound, dibastic alcohol compound and monomer into Row esterification and polycondensation reaction obtain the hydroxy-end capped aliphatic-aromatic copolyester of molten state；

The aromatic binary carboxylic acid class compound is terephthalic acid (TPA), dimethyl terephthalate (DMT), naphthalenedicarboxylic acid, naphthalenedicarboxylic acid It is one or more in dimethyl ester, biphenyl dicarboxylic acid, biphenyl dicarboxylic acid dimethyl ester and diethyl terephthalate；The aliphatic Dicarboxylic acids class compound is one or more in the aliphatic dicarboxylic acid class compound of C2~C40；The di-alcohols Compound is one or more in the dibastic alcohol compound of C2~C40；The monomer is multicomponent alcoholics compound, polynary carboxylic Acid compounds or polybasic carboxylic acid esters compound；

In the step a) amount of the total material of aromatic binary carboxylic acid class compound and aliphatic dicarboxylic acid class compound with The amount ratio of the substance of the dibastic alcohol compound is 1:0.8~1:2；The aromatic binary carboxylic acid class compound and aliphatic The amount ratio of the substance of dicarboxylic acids class compound is 10:90~90:10；

B) lactide is polymerize with the hydroxy-end capped aliphatic-aromatic copolyester of the obtained molten states of the step a) Reaction, obtains aliphatic-aromatic-polylactic-acid block copolymer.

2. aliphatic-aromatic-polylactic-acid block copolymer according to claim 1, which is characterized in that the step a) The temperature of middle esterification is 150 DEG C~230 DEG C；

The time of esterification is 1h~10h in the step a).

3. aliphatic-aromatic-polylactic-acid block copolymer according to claim 1, which is characterized in that the step a) The temperature of middle polycondensation reaction is 210 DEG C~290 DEG C；

The time of polycondensation reaction is 0.5h~48h in the step a)；

The pressure of polycondensation reaction is 10Pa~2000Pa in the step a).

4. aliphatic-aromatic-polylactic-acid block copolymer according to claim 1, which is characterized in that the step b) The temperature of middle polymerisation is 110 DEG C~180 DEG C；

The time of polymerisation is 3h~50h in the step b).

5. aliphatic-aromatic-polylactic-acid block copolymer according to claim 1, which is characterized in that the step b) The mass ratio of middle lactide and the hydroxy-end capped aliphatic-aromatic copolyester of molten state is 1:9~9:1.

6. a kind of aliphatic-aromatic-polylactic-acid block copolymer described in Claims 1 to 5 any one, which is characterized in that Aliphatic-aromatic-the polylactic-acid block copolymer has structure shown in Formulas I or Formula II：

Wherein, the p1=20~1400, n1=5~200, m1=5~200, x1=1~20, y1=1~20；

The p2=20~1400, n2=5~200, m2=5~200, x2=1~40；

The M₁And M₂Independently selected from the alkylene of C2~C40 or-R₃-O-R₄, the R₃And R₄Independently selected from C2~C20 Alkylene；

The A₁And A₂Independently selected from the alkylene of C2~C40；

The R₂Being Polycarboxylic acids removes the base after ester group except the group after decarboxylate or polybasic carboxylic acid esters compound Group；

The D₁And D₂Independently selected from aromatic binary carboxylic acid class compound except the group after decarboxylate；

The E₁And E₂Independently selected from structure shown in formula 101：

In formula 101, numbers of the q1 for branch, q1=1~50；

The E₃With structure shown in formula 102：

In formula 102, numbers of the q2 for branch, q2=1~50.

7. aliphatic-aromatic-polylactic-acid block copolymer according to claim 6, which is characterized in that the p1=50 ~1200, n1=10~150, m1=10~150, x1=1~15, y1=1~15, q1=2~20；

The p2=50~1200, n2=10~150, m2=10~150, x2=1~30, q2=2~20.