CN103804660B - A kind of unsaturated aliphatic-polylactic-acid block copolymer and preparation method thereof - Google Patents

A kind of unsaturated aliphatic-polylactic-acid block copolymer and preparation method thereof Download PDF

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CN103804660B
CN103804660B CN201410076475.9A CN201410076475A CN103804660B CN 103804660 B CN103804660 B CN 103804660B CN 201410076475 A CN201410076475 A CN 201410076475A CN 103804660 B CN103804660 B CN 103804660B
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acid
polylactic
block copolymer
unsaturated aliphatic
poly
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CN103804660A (en
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张宝
边新超
孙敬茹
李杲
陈学思
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Pulis Biotechnology Co ltd
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a kind of unsaturated aliphatic-polylactic-acid block copolymer, there is structure shown in formula (I).Structure containing long-chain unsaturated aliphatic polyester in the unsaturated aliphatic-polylactic-acid block copolymer of structure shown in formula provided by the invention (I), described long-chain unsaturated aliphatic polyester structure has flexibility, thus reduce the fragility of unsaturated aliphatic-polylactic-acid block copolymer, make unsaturated aliphatic-polylactic-acid block copolymer have better mechanical property; And, this structure is also given unsaturated aliphatic-polylactic-acid block copolymer and is had modifiable structural chain, that can modify again, that there is larger reactive behavior vinyl group is contained in this structural chain, radical polymerization or crosslinking reaction can be proceeded, increase mechanical strength, meet the requirement of various uses.Unsaturated aliphatic provided by the invention-polylactic-acid block copolymer elongation at break can up to 400%.

Description

A kind of unsaturated aliphatic-polylactic-acid block copolymer and preparation method thereof
Technical field
The invention belongs to technical field of organic synthesis, particularly relate to a kind of unsaturated aliphatic-polylactic-acid block copolymer and preparation method thereof.
Background technology
Along with the aggravation of environmental pollution, people propose higher requirement for the use of macromolecular material, while meeting materials'use performance, require macromolecular material environmentally safe.Poly(lactic acid) is based on biomass resource and degradable Green Polymer Material, nontoxic, nonirritant, there is the advantages such as good biocompatibility, Bioabsorbable, but containing a large amount of ester bonds in poly(lactic acid), wetting ability is poor, reduce the biocompatibility of poly(lactic acid) and other material, poly(lactic acid) is originally as simple linear polymer, and melt strength is low, and fragility is high, shock resistance is poor, limits it and widely uses.
For the above-mentioned shortcoming of poly(lactic acid), many researchers have carried out large quantity research to the modification of poly(lactic acid) in recent years.Publication number is that the Chinese patent of CN102977319A discloses a kind of degradable poly lactic acid di-block copolymer, its preparation method and the application in polydactyl acid thereof.Under inert atmosphere protection, the poly(lactic acid) being hydroxyl by end group that is dry, that dewater adds in reaction unit; Add diisocyanate again, stir at being heated to 185 DEG C ~ 190 DEG C and carry out reaction 5h ~ 8h; Add containing hydroxyl, degradable polymer again, stir at 185 DEG C ~ 190 DEG C and carry out reaction 1h ~ 2h; Add diisocyanate in the most backward reaction unit, stir and react at 185 DEG C ~ 190 DEG C, reaction can obtain degradable poly lactic acid di-block copolymer to being difficult to stirring.This degradable poly lactic acid di-block copolymer and polylactic resin consistency good, but its mechanical property is poor, and elongation at break can only reach 60%.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of unsaturated aliphatic-polylactic-acid block copolymer and preparation method thereof, unsaturated aliphatic-polylactic-acid block copolymer provided by the invention has higher mechanical property.
The invention provides a kind of unsaturated aliphatic-polylactic-acid block copolymer, there is structure shown in formula (I):
Wherein, m=5 ~ 200, n=5 ~ 200, p=10 ~ 500;
A, R and E are independently selected from alkylene or ether;
D and M is independently selected from alkylene.
Preferably, described m=10 ~ 180, n=10 ~ 180, p=20 ~ 350;
Preferably, described A, R and E are independently selected from the alkylene of carbonatoms 2 ~ 20 or ether.
Preferably, described D and M is independently selected from the alkylene of carbonatoms 2 ~ 50.
The invention provides a kind of preparation method of unsaturated aliphatic-polylactic-acid block copolymer, comprise the following steps:
A) saturated dicarboxylic acid compounds, saturated dibastic alcohol compound and unsaturated compound are carried out esterification and polycondensation, obtain the unsaturated aliphatic polyester of molten state;
Described saturated dicarboxylic acid compounds comprise in saturated dicarboxylic acid and saturated dicarboxylic acid derivative one or more;
Described unsaturated compound is the di-carboxylic acid compounds containing double bond or the dibastic alcohol compound containing double bond;
B) under oxygen-free environment, unsaturated aliphatic polyester and the rac-Lactide of the molten state described step a) obtained carry out polyreaction, obtain the unsaturated aliphatic-polylactic-acid block copolymer with structure shown in formula (I);
In formula (I), m=5 ~ 200, n=5 ~ 200, p=10 ~ 500;
A, R and E are independently selected from alkylene or ether;
D and M is independently selected from alkylene.
Preferably, described step a) in the carbonatoms of saturated dibastic alcohol compound be 2 ~ 20.
Preferably, described step a) in the carbonatoms of saturated dicarboxylic acid compounds be 2 ~ 50.
Preferably, described step a) in the carbonatoms of di-carboxylic acid compounds containing double bond be 4 ~ 50;
The carbonatoms of the described dibastic alcohol compound containing double bond is 4 ~ 20.
Preferably, described step a) in the mass ratio of saturated dicarboxylic acid compounds and saturated dibastic alcohol compound be 1:1 ~ 1:2;
The total mass ratio of the total mass of described saturated dicarboxylic acid compounds and the di-carboxylic acid compounds containing double bond and described saturated dibastic alcohol compound and the dibastic alcohol compound containing double bond is 1:1 ~ 1:2.
Preferably, described step a) in the temperature of esterification be 140 DEG C ~ 230 DEG C, the time of described esterification is 1h ~ 8h;
The temperature of described polycondensation is 210 DEG C ~ 290 DEG C, and the time of described polycondensation is 0.5h ~ 24h, and the pressure of described polycondensation is 10Pa ~ 300Pa.
Preferably, described step b) in the mass ratio of rac-Lactide and described unsaturated aliphatic polyester be 1:9 ~ 9:1.
Preferably, described step b) in the temperature of polyreaction be 110 DEG C ~ 180 DEG C;
Described step b) in time of polyreaction be 5h ~ 48h.
The invention provides a kind of unsaturated aliphatic-polylactic-acid block copolymer, there is structure shown in formula (I).Structure containing long-chain unsaturated aliphatic polyester in the unsaturated aliphatic-polylactic-acid block copolymer of structure shown in formula provided by the invention (I), described long-chain unsaturated aliphatic polyester structure has flexibility, thus reduce the fragility of unsaturated aliphatic-polylactic-acid block copolymer, make unsaturated aliphatic-polylactic-acid block copolymer have better mechanical property; And, this structure is also given unsaturated aliphatic-polylactic-acid block copolymer and is had modifiable structural chain, that can modify again, that there is larger reactive behavior vinyl group is contained in this structural chain, radical polymerization or crosslinking reaction can be proceeded, increase mechanical strength, meet the requirement of various uses.Experimental result shows: the elongation at break of unsaturated aliphatic-polylactic-acid block copolymer provided by the invention is up to 400%.
In addition, unsaturated aliphatic-polylactic-acid block copolymer provided by the invention to be polymerized with unsaturated aliphatic polyester by rac-Lactide and to obtain, unsaturated aliphatic-the copolymer of poly lactic acid obtained has good consistency to poly(lactic acid) or corresponding unsaturated aliphatic polyester, is conducive to the Application Areas expanding unsaturated aliphatic polyester and poly(lactic acid).The method preparing unsaturated aliphatic-polylactic-acid block copolymer provided by the invention, in whole preparation process, not with an organic solvent, decreases the pollution to environment; Saturated dibastic alcohol compound, saturated dicarboxylic acid compounds and unsaturated compound carry out esterification and polycondensation, obtain the unsaturated aliphatic polyester of molten state, the unsaturated aliphatic polyester of described molten state is without the need to purifying through dissolving sedimentation, direct and rac-Lactide carries out polyreaction, and not containing any moisture in the unsaturated aliphatic polyester of molten state, so this preparation method does not need through the drying that dewaters, simplify preparation technology, reduce cost, have broad application prospects and huge industrial value.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer that the embodiment of the present invention 1 obtains;
Fig. 2 is the stress-strain curve of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer that the embodiment of the present invention 1 obtains;
Fig. 3 is that the embodiment of the present invention 3 is not added BPO and added the change curve of complex viscosity with frequency of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer that BPO obtains.
Embodiment
The invention provides a kind of unsaturated aliphatic-polylactic-acid block copolymer, there is structure shown in formula (I):
In the present invention, described m=5 ~ 200, preferred m=10 ~ 150, more preferably m=50 ~ 100; Described n=5 ~ 200, preferred n=10 ~ 180, more preferably n=50 ~ 100; Described p=10 ~ 500, preferred p=20 ~ 350, more preferably p=150 ~ 300;
In the present invention, described R is selected from alkylene or ether, is preferably alkylene or the ether of carbonatoms 2 ~ 20, is more preferably ethylidene, butylidene, hexylidene, cyclohexylidene, butyl ether base or sub-decyl;
Described E is selected from alkylene or ether, is preferably alkylene or the ether of carbonatoms 2 ~ 20, is more preferably ethylidene, butylidene, hexylidene, cyclohexylidene, butyl ether base or sub-decyl;
Described A is selected from alkylene or ether, is preferably alkylene or the ether of carbonatoms 2 ~ 20, is more preferably ethylidene, butylidene, hexylidene, cyclohexylidene, butyl ether base or sub-decyl;
Described M is alkylene, is preferably the alkylene of carbonatoms 2 ~ 50, is more preferably ethylidene, butylidene, hexylidene, sub-decyl, vinylidene, propenylidene or sub-decene base;
Described D is alkylene, is preferably the alkylene of carbonatoms 2 ~ 50, is more preferably ethylidene, butylidene, hexylidene or sub-decyl.
Particularly, when R is butylidene (-(CH 2) 4-), M is vinylidene (-CH=CH-), and A is butylidene (-(CH 2) 4-), D is butylidene (-(CH 2) 2-), E is butylidene (-(CH 2) 4-) time, unsaturated aliphatic-polylactic-acid block copolymer has structure shown in formula (II):
In formula (II), m=5 ~ 200, n=5 ~ 200, p=10 ~ 500.
The invention provides a kind of preparation method of unsaturated aliphatic-polylactic-acid block copolymer, comprise the following steps:
A) saturated dicarboxylic acid compounds, saturated dibastic alcohol compound and unsaturated compound are carried out esterification and polycondensation, obtain the unsaturated aliphatic polyester of molten state;
Described saturated dicarboxylic acid compounds is one or more in saturated dicarboxylic acid and saturated dicarboxylic acid derivative;
Described unsaturated compound is the di-carboxylic acid compounds containing double bond or the dibastic alcohol compound containing double bond;
B) under oxygen-free environment, unsaturated aliphatic polyester and the rac-Lactide of the molten state described step a) obtained carry out polyreaction, obtain the unsaturated aliphatic-polylactic-acid block copolymer with structure shown in formula (I);
In formula (I), m=5 ~ 200, n=5 ~ 200, p=10 ~ 500;
A, R and E are independently selected from alkylene or ether;
D and M is independently selected from alkylene.
The method preparing unsaturated aliphatic-polylactic-acid block copolymer provided by the invention, in whole preparation process, not with an organic solvent, decreases the pollution to environment; The unsaturated aliphatic polyester of described molten state is without the need to purifying through dissolving sedimentation, direct and rac-Lactide carries out polyreaction, and not containing any moisture in the unsaturated aliphatic polyester of molten state, so this preparation method does not need through the drying that dewaters, simplify preparation technology, reduce cost, have broad application prospects and huge industrial value.
Saturated dicarboxylic acid compounds, saturated dibastic alcohol compound and unsaturated compound are carried out esterification and polycondensation by the present invention, obtain the unsaturated aliphatic polyester of molten state; Described saturated dicarboxylic acid compounds comprise in saturated dicarboxylic acid and saturated dicarboxylic acid derivative one or more; Described unsaturated compound comprises the di-carboxylic acid compounds containing double bond or the dibastic alcohol compound containing double bond.The present invention preferably carries out described esterification and polycondensation under anaerobic; The present invention realizes the environment of anaerobic preferably by nitrogen or rare gas element.The present invention does not have special restriction to described rare gas element, adopts rare gas element well known to those skilled in the art, is preferably argon gas.The order by merging of the present invention to described saturated dicarboxylic acid compounds, saturated dibastic alcohol compound and unsaturated compound does not have special restriction, preferably first by described saturated dicarboxylic acid compounds and the mixing of saturated dibastic alcohol compound, then add unsaturated compound wherein.
Described saturated dicarboxylic acid compounds, saturated dibastic alcohol compound and unsaturated compound preferably in the presence of a catalyst, are carried out esterification and polycondensation by the present invention.The present invention in order to distinguish the catalyzer in following technical proposals, by catalyzer called after first catalyzer used when esterification and polycondensation.The order by merging of the present invention to described saturated dicarboxylic acid compounds, saturated dibastic alcohol compound, unsaturated compound and the first catalyzer does not have special restriction, preferably by described saturated dicarboxylic acid compounds and saturated dibastic alcohol compound mixing, more successively with described unsaturated compound and the first catalyst mix.The container of the present invention to described esterification and polycondensation does not have special restriction, and can be reactor well known to those skilled in the art or flask, in an embodiment of the present invention, described reactor can be specially the reactor of band four ventage.In the present invention, described first catalyzer preferably include in the compound of the compound containing aluminium, the compound containing zinc, stanniferous compound, tosic acid and titaniferous one or more, more preferably comprise in tetrabutyl titanate, tin protochloride, isopropyl titanate, stannous octoate, zinc acetate and tosic acid one or more.
In the present invention, described saturated dicarboxylic acid compounds comprises one or more in saturated dicarboxylic acid and saturated dicarboxylic acid derivative, preferably including carbonatoms is one or more in the saturated dicarboxylic acid compounds of 2 ~ 50, more preferably propanedioic acid is comprised, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, dicarboxylic anhydride, one or more in the two alkyl ester of monoalkyl ester and diacid, most preferably comprise succinic acid, hexanodioic acid, sebacic acid, dicarboxylic anhydride, acid dimethyl, diethyl adipate, dipropyl malona-te, adipate, diacid diamyl ester, diacid binaryglycol ester, diisopropyl adipate, diacid diisoamyl ester, diacid di-isooctyl, diacid dibenzyl ester, pyrovinic acid and 2, one or more in 2-dimethyl succinic acid, the most preferably include dimethyl succinate, diethyl maleate, succinic acid, one or more in hexanodioic acid and sebacic acid.
In the present invention, it is one or more in the saturated dibastic alcohol compound of 2 ~ 20 that described saturated dibastic alcohol compound preferably includes carbonatoms, more preferably comprises ethylene glycol, propylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, 2,3-butanediol, BDO, 1,2-pentanediol, 1,3-pentanediol, Isosorbide-5-Nitrae-pentanediol, 1,5-PD, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexylene glycol, 1,3-hexylene glycol, Isosorbide-5-Nitrae-hexylene glycol, 1,5-hexylene glycol, 1,6-hexylene glycol, 2,5-hexylene glycol, phenyl-1，2-ethandiol, dipropylene glycol, Diethylene Glycol, triethylene glycol, 3-methoxyl group-1,2-PD, 1,7-heptanediol, 1,2-heptanediol, 1,8-ethohexadiol, 1,2-ethohexadiol, 1,11-undecane, decamethylene-glycol, 1,2-decanediol, 1,2-dodecanediol, 1,9-nonanediol, 1,12-dodecanediol, 1,13-tridecane diols, tripropylene glycol, 1,14-tetradecane diols, 1,15-pentadecane diols, 1,16-hexadecane diol, 1,17-heptadecane diols, 1,18-octadecandiol, 1,19-nonadecane glycol, 1,20-icosane diols, 1,2-ring pentanediol, 1,3-ring pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, the two methylol hexanaphthene of 1,2-, the two methylol hexanaphthene of 1,3-, Isosorbide-5-Nitrae-bis-methylol hexanaphthene, 1,2-double hydroxyethyl hexanaphthene, 1,3-double hydroxyethyl hexanaphthene, Isosorbide-5-Nitrae-double hydroxyethyl hexanaphthene, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexylene glycol, 2,5-dimethyl-2,5-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, 3 third glycol, polyoxyethylene glycol, one or more in polypropylene glycol and polytetramethylene ether diol, most preferably comprise glycol ether, 1,2-cyclohexanediol, 1,3-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 1,2-pentanediol, 1,3-pentanediol, Isosorbide-5-Nitrae-pentanediol, 1,5-PD, 2,3-pentanediol, 2,4-pentanediol, one or more in decamethylene-glycol and 1,2-decanediol.In the present invention, the mass ratio of described saturated dicarboxylic acid compounds and saturated dibastic alcohol compound is preferably 1:1 ~ 1:2, is more preferably 1:1.2 ~ 1:1.8, most preferably is 1:1.4 ~ 1:1.6.
In the present invention, described unsaturated compound comprises the di-carboxylic acid compounds containing double bond or the dibastic alcohol compound containing double bond.In the present invention, the described di-carboxylic acid compounds containing double bond is preferably the di-carboxylic acid compounds containing double bond of carbon atom number 4 ~ 50, more preferably comprises maleic acid, MALEIC ANHYDRIDE, fumaric acid, norbornene dicarboxylic anhydride, citraconic acid, methylfumaric acid, decene dicarboxylic acid, propene dicarboxylic acid dimethyl ester, propene dicarboxylic acid mono—n—butylester, monomethyl cis-butenedioic acid, cis-butenedioic acid mono ethyl maleate, Kunshun butene two acid mono-character ester, (E)-butenedioic acid dihexyl, (E)-butenedioic acid dibutylester, the two tridecyl ester of (E)-butenedioic acid, octene diacid, the chloro-(E)-butenedioic acid diethyl ester of 2-, (E)-butenedioic acid-dialkyl, tetradecene diacid dimethyl ester, muconic acid, trans dodecenoic acid, dimethyl maleate, 3-methylpentene acid dimethyl, propene dicarboxylic acid diethyl ester, dibenzyl fumarate, diethyl maleate, dibutyl maleate, amyl maleate, dioctyl maleate, trans-3-hexene diacid dimethyl ester, maleic acid rosin ester, maleic acid ethylhexyl, octadecene diacid, (E)-butenedioic acid list octadecyl ester, 2,3-dimethyl maleic anhydride, one or more in propene dicarboxylic acid and maleic acid ester, most preferably comprise dimethyl maleate, diethyl maleate, dibutyl maleate, maleic acid ethylhexyl, Kunshun butene two acid mono-character ester, dioctyl maleate, monomethyl cis-butenedioic acid, one or more in cis-butenedioic acid mono ethyl maleate and MALEIC ANHYDRIDE, the most preferably include MALEIC ANHYDRIDE, one or more in dimethyl maleate and diethyl maleate.In the present invention, in described (E)-butenedioic acid-dialkyl, the carbon atom number of alkyl is preferably 8 ~ 22, is more preferably 10 ~ 15.In the present invention, described saturated dicarboxylic acid compounds and be preferably 100:(0.01 ~ 1 containing the total mass of di-carboxylic acid compounds of double bond and the mass ratio of described first catalyzer), be more preferably 100:(0.1 ~ 0.8), most preferably be 100:(0.3 ~ 0.6).
The source of the present invention to above-mentioned unsaturated compound is not particularly limited, and adopts above-mentioned unsaturated compound well known to those skilled in the art.In the present invention, the preparation method of described maleic acid ester preferably includes following steps:
Alcohol compound and maleic anhydride are reacted, obtains maleic acid ester;
Described alcohol compound is one or more in dibasic alcohol.
The present invention does not have special restriction to the source of described alcohol compound and maleic anhydride and kind, adopts alcohol compound well known to those skilled in the art and maleic anhydride; Described alcohol compound is one or more in dibastic alcohol compound, and described dibasic alcohol can be straight dihydric alcohol, and can be branched chain dihydric alcohol, the present invention have special restriction to this yet.In the present invention, the mol ratio of described alcohol compound and maleic anhydride is preferably 1:1 ~ 1:2, is more preferably 1:1.2 ~ 1.8, most preferably is 1:1.3 ~ 1.7; The temperature of described reaction is preferably 30 DEG C ~ 150 DEG C, is more preferably 60 DEG C ~ 120 DEG C; The time of described reaction is preferably 3h ~ 24h, is more preferably 6 ~ 12h.
Particularly, when dibasic alcohol is straight dihydric alcohol, straight dihydric alcohol and maleic anhydride are obtained by reacting the maleic acid ester with structure shown in formula (III):
In formula (III), 20 >=q >=2.
In the present invention, the described dibastic alcohol compound containing double bond is preferably the dibastic alcohol compound containing double bond of carbon atom number 4 ~ 20, more preferably comprises 1,4-butylene glycol, 1, one or more in 2-butylene glycol and pungent ethylene glycol, most preferably are Isosorbide-5-Nitrae-butylene glycol; The total mass ratio of the total mass of described saturated dicarboxylic acid compounds and the di-carboxylic acid compounds containing double bond and described saturated dibastic alcohol compound and the dibastic alcohol compound containing double bond is preferably 1:1 ~ 1:2, be more preferably 1:1.2 ~ 1:1.8, most preferably be 1:1.4 ~ 1:1.6.
When described saturated dicarboxylic acid compounds, saturated dibastic alcohol compound and unsaturated compound are preferably carried out esterification by the present invention, collect the water that esterification generates, to no longer include liquid distillate time, then carry out polycondensation.The present invention preferably carries out esterification and polycondensation under the condition stirred.In the present invention, the temperature of described esterification is preferably 140 DEG C ~ 230 DEG C, is more preferably 160 DEG C ~ 200 DEG C, most preferably is 170 DEG C ~ 190 DEG C; The time of described esterification is preferably 1h ~ 8h, is more preferably 2h ~ 6h, most preferably is 3h ~ 5h; The temperature of described polycondensation is preferably 210 DEG C ~ 290 DEG C, is more preferably 230 DEG C ~ 270 DEG C, most preferably is 240 DEG C ~ 260 DEG C; The time of described polycondensation is preferably 0.5h ~ 24h, and the pressure of described polycondensation is preferably 10Pa ~ 300Pa, is more preferably 50Pa ~ 280Pa, most preferably is 150Pa ~ 250Pa.
The present invention carries out gel osmoticing chromatogram analysis to the unsaturated aliphatic polyester obtained, and detailed process is as follows:
Unsaturated aliphatic polyester is placed in gel permeation chromatograph measure, condition determination is: chloroform is moving phase, and flow velocity is 1mL/min, does universal calibration with the polystyrene standards of monodispersity.
Test result shows: the relative number average molecular weight of described unsaturated aliphatic polyester is 5kg/mol ~ 130kg/mol.
After obtaining the unsaturated aliphatic polyester of molten state, the present invention is under oxygen-free environment, the unsaturated aliphatic polyester of described molten state and rac-Lactide are carried out polyreaction, obtains the unsaturated aliphatic-polylactic-acid block copolymer with structure shown in formula (I).In the present invention, the unsaturated aliphatic polyester of described molten state as while polyreaction raw material, also as the initiator of polyreaction.The order of the present invention to the unsaturated aliphatic polyester of described molten state and rac-Lactide mixing does not have special restriction, preferably described rac-Lactide is placed in unsaturated aliphatic polyester.The present invention realizes the environment of anaerobic preferably by nitrogen or rare gas element.
The present invention carries out to be beneficial to reaction, preferably under the existence of the second catalyzer, the unsaturated aliphatic polyester of described molten state and rac-Lactide is carried out polyreaction.The order of the present invention to the unsaturated aliphatic polyester of described molten state, rac-Lactide and the second catalyst mix does not have special restriction, preferably described rac-Lactide is placed in the unsaturated aliphatic polyester of described molten state, then adds the second catalyzer wherein.In the present invention, described second catalyzer preferably include in aluminum isopropylate, divinyl zinc, tin protochloride and stannous octoate one or more, more preferably comprise in aluminum isopropylate and stannous octoate one or both; The mass ratio of described second catalyzer and rac-Lactide is preferably (0.01 ~ 1): 100, is more preferably (0.1 ~ 0.8): 100, most preferably is (0.3 ~ 0.6): 100.
The state of the present invention to described rac-Lactide does not have special restriction, is preferably dry rac-Lactide.In the present invention, described rac-Lactide preferably includes one or more in L-rac-Lactide, DL-rac-Lactide and meso-rac-Lactide; The mass ratio of described rac-Lactide and described unsaturated aliphatic polyester is preferably 1:9 ~ 9:1, is more preferably 1:8 ~ 1:2, most preferably is 1:7 ~ 1:3.
The temperature of described polyreaction is preferably 110 DEG C ~ 180 DEG C, is more preferably 120 DEG C ~ 170 DEG C, most preferably is 130 DEG C ~ 160 DEG C; The time of described polyreaction is preferably 5h ~ 48h, is more preferably 8h ~ 40h, most preferably is 15h ~ 25h.
The present invention is preferably after the unsaturated aliphatic polyester of described molten state and the polyreaction of rac-Lactide terminate, continue to heat up, vacuumize and remove unreacted monomer, obtain the unsaturated aliphatic-polylactic-acid block copolymer with structure shown in formula (I).In the present invention, described in the pressure that vacuumizes be preferably 200Pa ~ 255Pa, be more preferably 240Pa ~ 250Pa; The described temperature continuing to heat up is preferably 160 DEG C ~ 185 DEG C, is more preferably 175 DEG C ~ 180 DEG C.
After obtaining unsaturated aliphatic-polylactic-acid block copolymer, the present invention preferably adopts initiator to cause the polyreaction of described unsaturated aliphatic-polylactic-acid block copolymer, obtains cross-linking type unsaturated aliphatic-polylactic-acid block copolymer.In the present invention, described initiator preferably include in alkyl peroxide, peroxyester, Diisopropyl azodicarboxylate, peroxidation two acyl, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, benzoyl peroxide and methylethyl ketone peroxide one or more, more preferably comprise in the benzoyl peroxide tert-butyl ester, Diisopropyl azodicarboxylate and benzoyl peroxide one or more; The double bond that described initiator causes in unsaturated aliphatic-polylactic-acid block copolymer is polymerized; The consumption of described initiator is 0.01% ~ 1% of unsaturated aliphatic-polylactic-acid block copolymer.
In the present invention, the temperature of the polyreaction of described unsaturated aliphatic-polylactic-acid block copolymer is preferably 70 DEG C ~ 200 DEG C, is more preferably 100 DEG C ~ 190 DEG C, most preferably is 120 DEG C ~ 180 DEG C; The time of the polyreaction of described unsaturated aliphatic-polylactic-acid block copolymer is preferably 2min ~ 15min, is more preferably 3min ~ 10min.
Particularly, when saturated dicarboxylic acid compounds, saturated dibastic alcohol compound and the di-carboxylic acid compounds containing double bond carry out esterification and polycondensation, the unsaturated aliphatic polyester of molten state is obtained; Under oxygen-free environment, the unsaturated aliphatic polyester of described molten state and rac-Lactide carry out polyreaction, obtain the unsaturated aliphatic-polylactic-acid block copolymer with structure shown in formula (IV);
In formula (IV), described m 1=5 ~ 200, n 1=5 ~ 200, p 1=10 ~ 500;
Described R 1for alkylene or ether, described R 1it is the group after removing two hydroxyls in saturated dibastic alcohol compound;
Described M 1for alkylene, described M 1it is the group after removing two carboxyls or two ester groups in the di-carboxylic acid compounds containing double bond;
Described A 1for alkylene or ether, described A 1it is the group after removing two hydroxyls in saturated dibastic alcohol compound;
Described D 1for alkylene, shown D 1it is the group after removing two carboxyls or two ester groups in saturated dicarboxylic acid compounds;
Described E 1for alkylene or ether, described E 1it is the group after saturated dibastic alcohol compound removes two hydroxyls.
When saturated dicarboxylic acid compounds, saturated dibastic alcohol compound and the dibastic alcohol compound containing double bond carry out esterification and polycondensation, obtain the unsaturated aliphatic polyester of molten state; Under oxygen-free environment, the unsaturated aliphatic polyester of described molten state and rac-Lactide carry out polyreaction, obtain the unsaturated aliphatic-polylactic-acid block copolymer with structure shown in formula (V);
In formula (V), described m 2=5 ~ 200, n 2=5 ~ 200, p 2=10 ~ 500;
Described R 2for alkylene, described R 2it is the group after removing two hydroxyls in the dibastic alcohol compound containing double bond;
Described M 2for alkylene, described M 2it is the group after removing two carboxyls or two ester groups in saturated dicarboxylic acid compounds;
Described A 2for alkylene or ether, described A 2it is the group after removing two hydroxyls in saturated dibastic alcohol compound;
Described D 2for alkylene, shown D 2it is the group after removing two carboxyls or two ester groups in saturated dicarboxylic acid compounds;
Described E 2for alkylene or ether, described E 2be saturated dibastic alcohol compound or containing double bond dibastic alcohol compound in removing two hydroxyls after group.
In the present invention, rac-Lactide and unsaturated aliphatic polyester carry out being polymerized to mass polymerization, and at the temperature of the present invention's reaction, unsaturated aliphatic polyester and rac-Lactide are molten state, both itself can be used as solvent, therefore do not need to add any organic solvent in addition, reduce production cost, avoid organic solvent and to volatilize the harm that environment and human body are brought.
The present invention can stepwise synthesis, also can one pot process, carries out continuously.The intermediate product unsaturated aliphatic polyester that the present invention obtains does not need through any process, is directly used in next step and rac-Lactide ring-opening polymerization.In the present invention, described step a) and described step b) can react in same reaction vessel, also intermediate product can be transferred in another one reaction vessel after step a) terminates proceed next step reaction.
The present invention carries out gel osmoticing chromatogram analysis to the unsaturated aliphatic-polylactic-acid block copolymer with structure shown in formula (I) obtained, and detailed process is as follows:
Unsaturated aliphatic-polylactic-acid block copolymer is placed in gel permeation chromatograph and measures, and condition determination is: chloroform is moving phase, and flow velocity is 1mL/min, does universal calibration with the polystyrene standards of monodispersity.
Test result shows: the relative number average molecular weight of unsaturated aliphatic-polylactic-acid block copolymer that the present invention obtains is 10kg/mol ~ 100kg/mol; Relative molecular weight distribution is 1.0 ~ 2.0.
The present invention carries out the test of tensile property to the unsaturated aliphatic-polylactic-acid block copolymer with structure shown in formula (I) obtained, and detailed process is:
Unsaturated aliphatic-the polylactic-acid block copolymer of 70mm × 4mm × 1mm is placed on Instron4456 tensile testing machine and carries out Elongation test, rate of extension is 20mm/min, probe temperature is 23 DEG C, and carries out record to the elongation at break of unsaturated aliphatic-polylactic-acid block copolymer.
Test result shows: the elongation at break with the unsaturated aliphatic-polylactic-acid block copolymer of structure shown in formula (I) provided by the invention is up to 400%.
The invention provides a kind of unsaturated aliphatic-polylactic-acid block copolymer, there is structure shown in formula (I).Structure containing long-chain unsaturated aliphatic polyester in the unsaturated aliphatic-polylactic-acid block copolymer of structure shown in formula provided by the invention (I), described long-chain unsaturated aliphatic polyester structure has flexibility, thus reduce the fragility of unsaturated aliphatic-polylactic-acid block copolymer, make unsaturated aliphatic-polylactic-acid block copolymer have better mechanical property; And, this structure is also given unsaturated aliphatic-polylactic-acid block copolymer and is had modifiable structural chain, that can modify again, that there is larger reactive behavior vinyl group is contained in this structural chain, radical polymerization or crosslinking reaction can be proceeded, increase the requirement that mechanical strength meets various uses.Experimental result shows: the elongation at break of unsaturated aliphatic-polylactic-acid block copolymer provided by the invention is up to 400%.
In addition, unsaturated aliphatic-polylactic-acid block copolymer provided by the invention to be polymerized with rac-Lactide by unsaturated aliphatic polyester and to obtain, make the unsaturated aliphatic-polylactic-acid block copolymer obtained have good consistency to poly(lactic acid) or corresponding unsaturated aliphatic polyester, be conducive to the Application Areas expanding unsaturated aliphatic polyester and poly(lactic acid).The method preparing unsaturated aliphatic-polylactic-acid block copolymer provided by the invention, in whole preparation process, not with an organic solvent, decreases the pollution to environment; Saturated dibastic alcohol compound, saturated dicarboxylic acid compounds and unsaturated compound carry out esterification and polycondensation, obtain the unsaturated aliphatic polyester of molten state, the unsaturated aliphatic polyester of described molten state is without the need to purifying through dissolving sedimentation, direct and rac-Lactide carries out polyreaction, and not containing any moisture in the unsaturated aliphatic polyester of molten state, so this preparation method does not need through the drying that dewaters, simplify preparation technology, reduce cost, have broad application prospects and huge industrial value.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of unsaturated aliphatic-polylactic-acid block copolymer provided by the invention and preparation method thereof being described in detail, but they can not being interpreted as limiting the scope of the present invention.
Embodiment 1
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by 400g succinic acid, 600g butyleneglycol, 312g MALEIC ANHYDRIDE and 0.7g tetrabutyl titanate add after in reactor successively, 140 DEG C are warming up to reactor and reactant is stirred, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 210 DEG C, progressively raise the temperature of system, when reaching 210 DEG C, decompression step by step is to high vacuum state, the polycondensation of 3h is carried out when pressure is 250Pa, obtain the poly-succinic acid-butanediol-maleic acid butanediol ester of molten state.
The present invention's measuring technology scheme according to technique scheme carries out gel osmoticing chromatogram analysis to obtained multipolymer, the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester multipolymer is 13.0kg/mol, and relative molecular weight distribution is 1.73.
By the poly-succinic acid-butanediol of above-mentioned for 100g molten state-maleic acid butanediol ester, add rac-Lactide and the 0.4g stannous octoate of 400g drying wherein, then the mixture obtained is carried out polyreaction at 120 DEG C, mass polymerization is taked in reaction, 180 DEG C are warming up to after 10h, being evacuated to pressure is that 250Pa removes unreacted monomer, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out nuclear-magnetism qualification to the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer, as shown in Figure 1, Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer that the embodiment of the present invention 1 obtains to result.
The present invention carries out gel osmoticing chromatogram analysis to obtained poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer, analytical results shows: the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 33.0kg/mol, and relative molecular weight distribution is 1.53.
Nuclear-magnetism qualification and gel osmoticing chromatogram analysis test result show, the product that the present embodiment obtains has structure shown in formula (II).
The mechanical property of the present invention to poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer is tested, as shown in Figure 2, Fig. 2 is the stress-strain curve of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer that the embodiment of the present invention 1 obtains to the stress-strain curve obtained.
Fig. 2 shows, the elongation at break of the poly-succinic acid-butanediol that the embodiment of the present invention 1 obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 120%.
Embodiment 2
Poly-succinic acid-butanediol in Example 1-maleic acid butanediol ester copolymer 1 00g, adds rac-Lactide and the 0.2g stannous octoate (Sn (Otc) of 200g drying wherein 2), then the mixture obtained is reacted at 120 DEG C, reaction is such as formula shown in (a), mass polymerization is taked in this reaction, 180 DEG C are warming up to after 8h, vacuumize and remove unreacted monomer, pressure is 250Pa, obtains the poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer of molten state.
In formula (a), m=5 ~ 200, n=5 ~ 200, p=10 ~ 500.
The present invention's measuring technology scheme according to technique scheme carries out gel osmoticing chromatogram analysis to obtained multipolymer, the relative number average molecular weight of the poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer of the molten state obtained is 23.0kg/mol, and relative molecular weight distribution is 1.58.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 140%.
Embodiment 3
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by 400g succinic acid, 600g butyleneglycol, 312g MALEIC ANHYDRIDE and 0.7g tetrabutyl titanate add after in reactor successively, reactor is heated up and makes it reach 230 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 240 DEG C, progressively raise the temperature of system, polycondensation is vacuumized when reaching 240 DEG C, decompression step by step is to high vacuum state, pressure is that 250Pa carries out polycondensation, 2h discharging, obtain the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to the multipolymer of obtained molten state, analytical results shows: the relative number average molecular weight of the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state is 15.0kg/mol, and relative molecular weight distribution is 1.70.
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.4g stannous octoate of 400g drying wherein successively, then the mixture obtained is carried out polyreaction at 120 DEG C, mass polymerization is taked in reaction, 180 DEG C are warming up to after 10h, be evacuated to 250Pa and remove unreacted monomer, obtain poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention's measuring technology scheme according to technique scheme carries out gel osmoticing chromatogram analysis to obtained multipolymer, result shows: the relative number average molecular weight of the poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer of molten state is 36.0kg/mol, and relative molecular weight distribution is 1.55.
Utilize rotational rheometer to add benzoyl peroxide (BPO) front and back complex viscosity to poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer to test with the change of frequency, experiment parameter is: temperature T=182 DEG C, sweep rate=0.1S -1~ 100S -1the result obtained as shown in Figure 3, Fig. 3 is that the embodiment of the present invention 3 is not added BPO and added the change curve of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer complex viscosity of obtaining of BPO with frequency, wherein, curve 1 is do not add poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer complex viscosity that BPO obtains change curve with frequency, and curve 2 is add poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer complex viscosity that BPO obtains change curve with frequency.
As seen from Figure 2, after adding BPO, the complex viscosity of the poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer of the molten state obtained increases greatly.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 125%.
Embodiment 4
Get poly-succinic acid-butanediol in 100g embodiment 3-maleic acid butanediol ester multipolymer, add rac-Lactide and the 0.3g stannous octoate of 300g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, 180 DEG C are warming up to after 10h, vacuumize and remove unreacted monomer, pressure is 250Pa, obtains the poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 30.0kg/mol, and relative molecular weight distribution is 1.54.
The present invention tests according to the mechanical property of technique scheme to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 135%.
Embodiment 5
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by 400g succinic acid, 600g butyleneglycol, 312g MALEIC ANHYDRIDE and 0.7g aluminum isopropylate add after in reactor successively, reactor is heated up and makes it reach 150 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 230 DEG C, progressively raise the temperature of system, polycondensation is vacuumized when reaching 230 DEG C, decompression step by step is to high vacuum state, carry out polycondensation, pressure is 250Pa, 2h discharging, obtain the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer is 19.0kg/mol, and relative molecular weight distribution is 1.78.
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.4g stannous octoate of 400g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 12h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, result shows: the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 55.0kg/mol, and relative molecular weight distribution is 1.45.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 130%.
Embodiment 6
Poly-succinic acid-butanediol-maleic acid butanediol ester copolymer 1 the 00g of molten state in Example 5, add rac-Lactide and the 0.2g stannous octoate of 200g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, be warming up to 180 DEG C after 8h and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 37.0kg/mol, and relative molecular weight distribution is 1.65.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 150%.
Embodiment 7
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by 500g succinic acid, 600g butyleneglycol, 228g MALEIC ANHYDRIDE and 0.7g zinc acetate add after in reactor successively, reactor is heated up and makes it reach 140 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 215 DEG C, progressively raise the temperature of system, decompression step by step is vacuumized to high vacuum state when reaching 215 DEG C, pressure is that 250Pa carries out polycondensation, 3h discharging, obtain the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state.
Poly-succinic acid-butanediol-maleic acid butanediol ester the multipolymer of the present invention to the molten state obtained carries out gel osmoticing chromatogram analysis, analytical results shows: the relative number average molecular weight of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester multipolymer is 14.0kg/mol, and relative molecular weight distribution is 1.75.
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.4g stannous octoate of 400g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 6h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 35.0kg/mol, and relative molecular weight distribution is 1.53.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 127%.
Embodiment 8
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state described in 100g embodiment 7, add rac-Lactide and the 0.2g stannous octoate of 200g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, be warming up to 180 DEG C after 8h and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: relative number average molecular weight is 25.0kg/mol, and relative molecular weight distribution is 1.62.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 145%.
Embodiment 9
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, 500g succinic acid, 693g pentanediol, 228g MALEIC ANHYDRIDE and 0.7g stannous octoate are added after in reactor successively, reactor is heated up and makes it reach 150 DEG C and stir reactant, simultaneously collect reaction generate water, when reaction no longer include liquid distillate time, temperature of reaction is set to 215 DEG C, progressively raise the temperature of system, when reaching 215 DEG C, vacuumize polycondensation.Decompression step by step, to high vacuum state, carries out polycondensation, and pressure is 250Pa, 3h discharging, obtains the poly-succinic pentanediol-maleic acid pentadiol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic pentanediol-maleic acid pentadiol ester multipolymer is 16.0kg/mol, and relative molecular weight distribution is 1.77.
Get the poly-succinic pentanediol-maleic acid pentadiol ester multipolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.4g stannous octoate of 400g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 9h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic pentanediol-maleic acid pentadiol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 37.0kg/mol, and relative molecular weight distribution is 1.65.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 121%.
Embodiment 10
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by succinic acid 500g, pentanediol 330g, 1, 4-butylene glycol 100g and tetrabutyl titanate 0.7g adds after in reactor successively, reactor is heated up and makes it reach 150 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 220 DEG C, progressively raise the temperature of system, polycondensation is vacuumized when reaching 220 DEG C, decompression step by step is to high vacuum state, carry out polycondensation, pressure is 300Pa, 3h discharging, obtain the poly-succinic pentanediol-succinic acid butylene glycol ester copolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: number average mol weight is 17.0kg/mol, and relative molecular weight distribution is 1.79.
Get the poly-succinic pentanediol-succinic acid butylene glycol ester copolymer 100g of above-mentioned molten state, add dry rac-Lactide 400g and stannous octoate 0.4g wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 8h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic pentanediol-succinic acid butylene glycol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic pentanediol-succinic acid butylene glycol ester-polylactic-acid block copolymer is 36.0kg/mol, and relative molecular weight distribution is 1.68.
The mechanical property of the present invention to product is tested, and test result shows: the elongation at break of the poly-succinic pentanediol that the present embodiment obtains-succinic acid butylene glycol ester-polylactic-acid block copolymer is 122%.
Embodiment 11
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by dimethyl succinate 620g, pentanediol 693g, MALEIC ANHYDRIDE 228g and tetrabutyl titanate 0.7g adds after in reactor successively, reactor is heated up and makes it reach 150 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 230 DEG C, progressively raise the temperature of system, polycondensation is vacuumized when reaching 230 DEG C, decompression step by step is to high vacuum state, carry out polycondensation, pressure is 200Pa, 3h discharging, obtain the poly-succinic pentanediol-maleic acid pentadiol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic pentanediol-maleic acid pentadiol ester multipolymer is 19.0kg/mol, and relative molecular weight distribution is 1.85.
Get the poly-succinic pentanediol-maleic acid pentadiol ester copolymer 1 00g of above-mentioned molten state, add dry rac-Lactide 300g and stannous octoate 0.4g wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, 175 DEG C are warming up to after 9h, vacuumize and remove unreacted monomer, pressure is 240Pa, obtains poly-succinic pentanediol-maleic acid pentadiol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, result shows: the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 40.0kg/mol, and relative molecular weight distribution is 1.48.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic pentanediol that the present embodiment obtains-maleic acid pentadiol ester-polylactic-acid block copolymer is 130%.
Embodiment 12
Get the poly-succinic pentanediol-maleic acid pentadiol ester multipolymer of molten state in 100g embodiment 11, add rac-Lactide and the 0.2g stannous octoate of 200g drying wherein, then the mixture obtained is reacted at 110 DEG C, mass polymerization is taked in reaction, 180 DEG C are warming up to after 10h, vacuumize and remove unreacted monomer, pressure is 250Pa, obtains poly-succinic pentanediol-maleic acid pentadiol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic pentanediol-maleic acid pentadiol ester-polylactic-acid block copolymer is 36.0kg/mol, and relative molecular weight distribution is 1.55.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic pentanediol that the present embodiment obtains-maleic acid pentadiol ester-polylactic-acid block copolymer is 151%.
Embodiment 13
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by 500g succinic acid, 600g butyleneglycol, 400g diethyl maleate and 0.7g tetrabutyl titanate add after in reactor successively, reactor is heated up and makes it reach 160 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 215 DEG C, progressively raise the temperature of system, polycondensation is vacuumized when reaching 215 DEG C, decompression step by step is to high vacuum state, pressure is 150Pa, carry out polycondensation, 5h discharging, obtain the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer is 22.0kg/mol, and relative molecular weight distribution is 1.87.
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of the above-mentioned molten state of 100g, add rac-Lactide and the sub-tin of 0.4g octoate catalyst of 400g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 10h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 56.0kg/mol, and relative molecular weight distribution is 1.49.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 116%.
Embodiment 14
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state in 100g embodiment 13, add rac-Lactide and the 0.2g stannous octoate of 200g drying wherein, then the mixture obtained is reacted at 180 DEG C, mass polymerization is taked in reaction, after 10h, be warming up to 185 DEG C and vacuumize the unreacted monomer of removal, pressure is 230Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer is 39.0kg/mol, and relative molecular weight distribution is 1.59.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 156%.
Embodiment 15
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by 400g succinic acid, 720g butyleneglycol, 547g diethyl maleate and 0.7g tetrabutyl titanate add after in reactor successively, reactor is heated up and makes it reach 140 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 210 DEG C, progressively raise the temperature of system, when reaching 210 DEG C, decompression step by step is to high vacuum state, pressure is 100Pa, carry out polycondensation, 8h discharging, obtain the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state is 17.0kg/mol, and relative molecular weight distribution is 1.69.
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.04g stannous octoate of 400g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 10h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 36.0kg/mol, and relative molecular weight distribution is 1.56.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 117%.
Embodiment 16
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state in 100g embodiment 15, add rac-Lactide and the 2g stannous octoate of 200g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 2h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 240Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer is 26.0kg/mol, and relative molecular weight distribution is 1.58.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 139%.
Embodiment 17
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, and then when passing into nitrogen, by 400g succinic acid, 720g butyleneglycol, 547g diethyl maleate and 0.7g tetrabutyl titanate add after in reactor successively, reactor is heated up and makes it reach 150 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 210 DEG C, progressively raise the temperature of system, when reaching 210 DEG C, decompression step by step is to high vacuum state, pressure is 250Pa, carry out polycondensation, 5h discharging, obtain the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer is 16.0kg/mol, and relative molecular weight distribution is 1.77.
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.4g stannous octoate of 400g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, be warming up to 180 DEG C after 5h and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtain poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer, then nitrogen is filled with, 1g benzoyl peroxide is added under whipped state, reaction 3min, obtain cross-linking type poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer is 35.0kg/mol, and relative molecular weight distribution is 1.58.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 156%.
Embodiment 18
Get the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state described in 100g embodiment 17, add 300g rac-Lactide and 0.3g stannous octoate wherein, then react at 120 DEG C, mass polymerization is taked in reaction, after 8h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer is 30.0kg/mol, and relative molecular weight distribution is 1.64.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 138%.
Embodiment 19
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, and then when passing into nitrogen, by 495g hexanodioic acid, 720g butyleneglycol, 312g MALEIC ANHYDRIDE and 0.7g tetrabutyl titanate add after in reactor successively, reactor is heated up and makes it reach 150 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 230 DEG C, progressively raise the temperature of system, decompression step by step is vacuumized to high vacuum state when reaching 230 DEG C, pressure is 250Pa, carry out polycondensation, 3h discharging, obtain the polybutyleneadipate-maleic acid butanediol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of polybutyleneadipate-maleic acid butanediol ester multipolymer is 22.0kg/mol, and relative molecular weight distribution is 1.88.
Get the polybutyleneadipate-maleic acid butanediol ester multipolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.4g stannous octoate of 400g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 8h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and the relative number average molecular weight of the poly-succinic acid-butanediol obtained-maleic acid butanediol ester-polylactic-acid block copolymer is 56.0kg/mol, and relative molecular weight distribution is 1.49.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 124%.
Embodiment 20
Get the polybutyleneadipate-maleic acid butanediol ester multipolymer of molten state described in 100g embodiment 19, add rac-Lactide and the 0.2g stannous octoate of 200g drying wherein, then react at 120 DEG C, mass polymerization is taked in reaction, after 9h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains polybutyleneadipate-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of polybutyleneadipate-maleic acid butanediol ester-polylactic-acid block copolymer is 39.0kg/mol, and relative molecular weight distribution is 1.48.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the polybutyleneadipate that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 146%.
Embodiment 21
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, sebacic acid 855g, butyleneglycol 720g, MALEIC ANHYDRIDE 228g and tetrabutyl titanate 0.7g are added after in reactor successively, reactor is heated up and makes it reach 140 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 215 DEG C, progressively raise the temperature of system, when reaching 215 DEG C, vacuumize polycondensation.Decompression step by step is to high vacuum state, and pressure is 250Pa, carries out polycondensation, 3h discharging, obtains the poly-sebacic acid butyleneglycol-maleic acid butanediol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-sebacic acid butyleneglycol-maleic acid butanediol ester multipolymer is 18.0kg/mol, and relative molecular weight distribution is 1.76.
Get the poly-sebacic acid butyleneglycol-maleic acid butanediol ester multipolymer of the above-mentioned molten state of 100g, add dry rac-Lactide 400g and stannous octoate 0.4g wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, be warming up to 180 DEG C after 8h and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-sebacic acid butyleneglycol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and the relative number average molecular weight of the poly-sebacic acid butyleneglycol-maleic acid butanediol ester-polylactic-acid block copolymer obtained is 43.0kg/mol, and relative molecular weight distribution is 1.58.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of poly-sebacic acid butyleneglycol-maleic acid butanediol ester-polylactic-acid block copolymer that the present embodiment obtains is 120%.
Embodiment 22
By the poly-sebacic acid butyleneglycol-maleic acid butanediol ester multipolymer of molten state in 100g embodiment 21, add rac-Lactide and the 0.2g stannous octoate of 200g drying, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 10h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-sebacic acid butyleneglycol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained poly-sebacic acid butyleneglycol-maleic acid butanediol ester-polylactic-acid block copolymer, analytical results shows: the relative number average molecular weight of poly-sebacic acid butyleneglycol-maleic acid butanediol ester-polylactic-acid block copolymer that the present embodiment obtains is 29.0kg/mol, and relative molecular weight distribution is 1.68.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of poly-sebacic acid butyleneglycol-maleic acid butanediol ester-polylactic-acid block copolymer that the present embodiment obtains is 149%.
Embodiment 23
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by hexanodioic acid 618g, decanediol 1400g, MALEIC ANHYDRIDE 228g and tetrabutyl titanate 0.7g adds after in reactor successively, reactor is heated up and makes it reach 150 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 215 DEG C, progressively raise the temperature of system, polycondensation is vacuumized when reaching 215 DEG C, decompression step by step is to high vacuum state, pressure is 250Pa, carry out polycondensation, 7h discharging, obtain the poly-hexanodioic acid decanediol-maleic acid decanediol ester copolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of the poly-hexanodioic acid decanediol-maleic acid decanediol ester copolymer of molten state is 19.0kg/mol, and relative molecular weight distribution is 1.67.
Get the poly-hexanodioic acid decanediol-maleic acid decanediol ester copolymer 100g of above-mentioned molten state, add dry rac-Lactide 400g and stannous octoate 0.4g wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, be warming up to 180 DEG C after 10h and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-hexanodioic acid decanediol-maleic acid decanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained poly-hexanodioic acid decanediol-maleic acid decanediol ester-polylactic-acid block copolymer, analytical results shows: poly-hexanodioic acid decanediol-maleic acid decanediol ester-polylactic-acid block copolymer relative number average molecular weight that the present embodiment obtains is 50.0kg/mol, and relative molecular weight distribution is 1.55.
The mechanical property of the present invention to poly-hexanodioic acid decanediol-maleic acid decanediol ester-polylactic-acid block copolymer is tested, and test result shows: the elongation at break of poly-hexanodioic acid decanediol-maleic acid decanediol ester-polylactic-acid block copolymer that the present embodiment obtains is 122%.
Embodiment 24
Get the poly-hexanodioic acid decanediol-maleic acid decanediol ester copolymer of molten state in 100g embodiment 23, add rac-Lactide and the 0.3g stannous octoate of 300g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, be warming up to 180 DEG C after 8h and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-hexanodioic acid decanediol-maleic acid decanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, analytical results shows: the relative number average molecular weight of poly-hexanodioic acid decanediol-maleic acid decanediol ester-polylactic-acid block copolymer that the present embodiment obtains is 35.0kg/mol, and relative molecular weight distribution is 1.59.
The mechanical property of the present invention to product is tested, and test result shows: the elongation at break of poly-hexanodioic acid decanediol-maleic acid decanediol ester copolymer that the present embodiment obtains is 142%.
Embodiment 25
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by Succinic anhydried 420g, butyleneglycol 720g, diethyl maleate 400g and tetrabutyl titanate 0.7g adds after in reactor successively, reactor is heated up and makes it reach 150 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 230 DEG C, progressively raise the temperature of system, polycondensation is vacuumized when reaching 230 DEG C, decompression step by step is to high vacuum state, pressure is 250Pa, carry out polycondensation, 2h discharging, obtain the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the poly-succinic acid-butanediol-maleic acid butanediol ester multipolymer relative number average molecular weight of molten state is 23.0kg/mol, and relative molecular weight distribution is 1.88.
Get the poly-succinic acid-butanediol-maleic acid butanediol ester copolymer 1 00g of above-mentioned molten state, add dry rac-Lactide 400g and stannous octoate 0.4g wherein, then the mixture obtained is carried out polyreaction at 120 DEG C, mass polymerization is taked in reaction, be warming up to 180 DEG C after 6h and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer is 57.0kg/mol, and relative molecular weight distribution is 1.45.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 125%.
Embodiment 26
Get poly-succinic acid-butanediol in 100g embodiment 25-maleic acid butanediol ester multipolymer, add rac-Lactide and the 0.2g stannous octoate of 200g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, be warming up to 180 DEG C after 8h and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains the poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained multipolymer, and analytical results shows: the relative number average molecular weight of poly-succinic acid-butanediol-maleic acid butanediol ester-polylactic-acid block copolymer is 38.0kg/mol, and relative molecular weight distribution is 1.52.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the poly-succinic acid-butanediol that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 153%.
Embodiment 27
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by 618g hexanodioic acid, 720g butyleneglycol, 400g diethyl maleate and 0.7g tetrabutyl titanate add after in reactor successively, reactor is heated up and makes it reach 160 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 215 DEG C, progressively raise the temperature of system, decompression step by step is vacuumized to high vacuum state when reaching 215 DEG C, pressure is 250Pa, carry out polycondensation, 8h discharging, obtain the polybutyleneadipate-maleic acid butanediol ester multipolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained polybutyleneadipate-maleic acid butanediol ester multipolymer, analytical results shows: the relative number average molecular weight of polybutyleneadipate-maleic acid butanediol ester multipolymer is 23.0kg/mol, and relative molecular weight distribution is 1.77.
Get the polybutyleneadipate-maleic acid butanediol ester multipolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.4g stannous octoate of 400g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 16h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains polybutyleneadipate-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to the polybutyleneadipate obtained-maleic acid butanediol ester-polylactic-acid block copolymer, analytical results shows: the relative number average molecular weight of the polybutyleneadipate that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 59.0kg/mol, and relative molecular weight distribution is 1.48.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the polybutyleneadipate that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 126%.
Embodiment 28
Get the polybutyleneadipate-maleic acid butanediol ester multipolymer of molten state described in 100g embodiment 27, add rac-Lactide and the 0.05g stannous octoate of 50g drying wherein, then the mixture obtained is reacted at 140 DEG C, mass polymerization is taked in reaction, after 10h, be warming up to 160 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtain polybutyleneadipate-maleic acid butanediol ester-polylactic-acid block copolymer, be filled with nitrogen again, 0.3g Diisopropyl azodicarboxylate is added under whipped state, reaction 10min, obtain cross-linking type polybutyleneadipate-maleic acid butanediol ester-polylactic-acid block copolymer.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of the polybutyleneadipate that the present embodiment obtains-maleic acid butanediol ester-polylactic-acid block copolymer is 400%.
Embodiment 29
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by 618g hexanodioic acid, 850g glycol ether, 400g diethyl maleate and 0.7g tetrabutyl titanate add after in reactor successively, reactor is heated up and makes it reach 160 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 220 DEG C, progressively raise the temperature of system, decompression step by step is vacuumized to high vacuum state when reaching 220 DEG C, pressure is 250Pa, carry out polycondensation, 4h discharging, obtain the poly-hexanodioic acid glycol ether-maleic acid glycol ether ester copolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained poly-hexanodioic acid glycol ether-maleic acid glycol ether ester copolymer, analytical results shows: the relative number average molecular weight of poly-hexanodioic acid glycol ether-maleic acid glycol ether ester copolymer is 25.0kg/mol, and relative molecular weight distribution is 1.79.
Get the poly-hexanodioic acid glycol ether-maleic acid glycol ether ester copolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.2g stannous octoate of 200g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 18h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-hexanodioic acid glycol ether-maleic acid glycol ether ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to the poly-hexanodioic acid glycol ether-maleic acid glycol ether ester-polylactic-acid block copolymer obtained, analytical results shows: the relative number average molecular weight of poly-hexanodioic acid glycol ether-maleic acid glycol ether ester-polylactic-acid block copolymer that the present embodiment obtains is 40.0kg/mol, and relative molecular weight distribution is 1.57.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of poly-hexanodioic acid glycol ether-maleic acid glycol ether ester-polylactic-acid block copolymer that the present embodiment obtains is 180%.
Embodiment 30
By the reactor of 2L with four ventages through vacuum nitrogen filling air cooling repeatedly but, then when passing into nitrogen, by 618g hexanodioic acid, 1160g cyclohexanediol, 400g diethyl maleate and 0.7g tetrabutyl titanate add after in reactor successively, reactor is heated up and makes it reach 160 DEG C and stir reactant, collect the water that reaction generates simultaneously, when reaction no longer include liquid distillate time, temperature of reaction is set to 220 DEG C, progressively raise the temperature of system, decompression step by step is vacuumized to high vacuum state when reaching 220 DEG C, pressure is 250Pa, carry out polycondensation, 5h discharging, obtain the poly-hexanodioic acid cyclohexanediol-maleic acid cyclohexanediol ester copolymer of molten state.
The present invention carries out gel osmoticing chromatogram analysis to obtained poly-hexanodioic acid cyclohexanediol-maleic acid cyclohexanediol ester copolymer, analytical results shows: the relative number average molecular weight of poly-hexanodioic acid cyclohexanediol-maleic acid cyclohexanediol ester copolymer is 24.0kg/mol, and relative molecular weight distribution is 1.84.
Get the poly-hexanodioic acid cyclohexanediol-maleic acid cyclohexanediol ester copolymer of the above-mentioned molten state of 100g, add rac-Lactide and the 0.2g stannous octoate of 200g drying wherein, then the mixture obtained is reacted at 120 DEG C, mass polymerization is taked in reaction, after 15h, be warming up to 180 DEG C and vacuumize the unreacted monomer of removal, pressure is 250Pa, obtains poly-hexanodioic acid cyclohexanediol-maleic acid cyclohexanediol ester-polylactic-acid block copolymer.
The present invention carries out gel osmoticing chromatogram analysis to the poly-hexanodioic acid cyclohexanediol-maleic acid cyclohexanediol ester-polylactic-acid block copolymer obtained, analytical results shows: the relative number average molecular weight of poly-hexanodioic acid cyclohexanediol-maleic acid cyclohexanediol ester-polylactic-acid block copolymer that the present embodiment obtains is 41.0kg/mol, and relative molecular weight distribution is 1.59.
The present invention carries out Mechanics Performance Testing to product, and test result shows: the elongation at break of poly-hexanodioic acid cyclohexanediol-maleic acid cyclohexanediol ester-polylactic-acid block copolymer that the present embodiment obtains is 175%.
As seen from the above embodiment, the invention provides a kind of unsaturated aliphatic-polylactic-acid block copolymer, there is structure shown in formula (I).Structure containing long-chain unsaturated aliphatic polyester in the unsaturated aliphatic-polylactic-acid block copolymer of structure shown in formula provided by the invention (I), described long-chain unsaturated aliphatic polyester structure has flexibility, thus reduce the fragility of unsaturated aliphatic-polylactic-acid block copolymer, make unsaturated aliphatic-polylactic-acid block copolymer have better mechanical property; And this structure is also given unsaturated aliphatic-polylactic-acid block copolymer and is had modifiable structural chain, that can modify again, that there is larger reactive behavior vinyl group is contained in this structural chain, radical polymerization or crosslinking reaction can be proceeded, increase the requirement that mechanical strength meets various uses.Experimental result shows: the elongation at break of unsaturated aliphatic-polylactic-acid block copolymer provided by the invention is up to 400%.
In addition, unsaturated aliphatic-polylactic-acid block copolymer provided by the invention to be polymerized with unsaturated aliphatic polyester by rac-Lactide and to obtain, make the unsaturated aliphatic-copolymer of poly lactic acid obtained have good consistency to poly(lactic acid) or corresponding unsaturated aliphatic polyester, be conducive to the Application Areas expanding unsaturated aliphatic polyester and poly(lactic acid).The method preparing unsaturated aliphatic-polylactic-acid block copolymer provided by the invention, in whole preparation process, not with an organic solvent, decreases the pollution to environment; Saturated dibastic alcohol compound, saturated dicarboxylic acid compounds and unsaturated compound carry out esterification and polycondensation, obtain the unsaturated aliphatic polyester of molten state, the unsaturated aliphatic polyester of described molten state is without the need to purifying through dissolving sedimentation, direct and rac-Lactide carries out polyreaction, and not containing any moisture in the unsaturated aliphatic polyester of molten state, so this preparation method does not need through the drying that dewaters, simplify preparation technology, reduce cost, have broad application prospects and huge industrial value.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (10)

1. unsaturated aliphatic-polylactic-acid block copolymer, has structure shown in formula (I):
In formula (I), m=5 ~ 200, n=5 ~ 200, p=10 ~ 500;
R, A and E remove the group after two hydroxyls independently selected from saturated dibastic alcohol compound, M is the group after the di-carboxylic acid compounds containing double bond removes two carboxyls or two ester groups, and D is the group after saturated dicarboxylic acid compounds removes two carboxyls or two ester groups;
Or, R is the group after the dibastic alcohol compound containing double bond removes two hydroxyls, M and D removes the group after two carboxyls or two ester groups independently selected from saturated dicarboxylic acid compounds, A is the group after removing two hydroxyls in saturated dibastic alcohol compound, and E is the group after saturated dibastic alcohol compound or the dibastic alcohol compound containing double bond remove two hydroxyls.
2. unsaturated aliphatic-polylactic-acid block copolymer according to claim 1, is characterized in that, m=10 ~ 150 described in formula (I), n=10 ~ 180, p=20 ~ 350.
3. a preparation method for unsaturated aliphatic-polylactic-acid block copolymer, comprises the following steps:
A) saturated dicarboxylic acid compounds, saturated dibastic alcohol compound and unsaturated compound are carried out esterification and polycondensation, obtain the unsaturated aliphatic polyester of molten state;
Described saturated dicarboxylic acid compounds comprise in saturated dicarboxylic acid and saturated dicarboxylic acid derivative one or more;
Described unsaturated compound is the di-carboxylic acid compounds containing double bond or the dibastic alcohol compound containing double bond;
B) under oxygen-free environment, unsaturated aliphatic polyester and the rac-Lactide of the molten state described step a) obtained carry out polyreaction, obtain the unsaturated aliphatic-polylactic-acid block copolymer with structure shown in formula (I);
In formula (I), m=5 ~ 200, n=5 ~ 200, p=10 ~ 500;
R, A and E remove the group after two hydroxyls independently selected from saturated dibastic alcohol compound, M is the group after the di-carboxylic acid compounds containing double bond removes two carboxyls or two ester groups, and D is the group after saturated dicarboxylic acid compounds removes two carboxyls or two ester groups;
Or, R is the group after the dibastic alcohol compound containing double bond removes two hydroxyls, M and D removes the group after two carboxyls or two ester groups independently selected from saturated dicarboxylic acid compounds, A is the group after removing two hydroxyls in saturated dibastic alcohol compound, and E is the group after saturated dibastic alcohol compound or the dibastic alcohol compound containing double bond remove two hydroxyls.
4. preparation method according to claim 3, is characterized in that, described step a) in the carbonatoms of saturated dibastic alcohol compound be 2 ~ 20.
5. preparation method according to claim 3, is characterized in that, described step a) in the carbonatoms of saturated dicarboxylic acid compounds be 2 ~ 50.
6. preparation method according to claim 3, is characterized in that, described step a) in the carbonatoms of di-carboxylic acid compounds containing double bond be 4 ~ 50;
The carbonatoms of the described dibastic alcohol compound containing double bond is 4 ~ 20.
7. preparation method according to claim 3, is characterized in that, described step a) in the mass ratio of saturated dicarboxylic acid compounds and saturated dibastic alcohol compound be 1:1 ~ 1:2;
The total mass ratio of the total mass of described saturated dicarboxylic acid compounds and the di-carboxylic acid compounds containing double bond and described saturated dibastic alcohol compound and the dibastic alcohol compound containing double bond is 1:1 ~ 1:2.
8. preparation method according to claim 3, is characterized in that, described step a) in the temperature of esterification be 140 DEG C ~ 230 DEG C, the time of described esterification is 1h ~ 8h;
The temperature of described polycondensation is 210 DEG C ~ 290 DEG C, and the time of described polycondensation is 0.5h ~ 24h, and the pressure of described polycondensation is 10Pa ~ 300Pa.
9. preparation method according to claim 3, is characterized in that, described step b) in the mass ratio of rac-Lactide and described unsaturated aliphatic polyester be 1:9 ~ 9:1.
10. preparation method according to claim 3, is characterized in that, described step b) in the temperature of polyreaction be 110 DEG C ~ 180 DEG C;
Described step b) in time of polyreaction be 5h ~ 48h.
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CN105368019B (en) * 2014-08-29 2017-04-19 中国科学院长春应用化学研究所 Polylactic acid stereo complex
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CN113817148B (en) * 2021-09-14 2023-05-26 内蒙古农业大学 Polylactic acid copolymer, preparation method and application thereof, and preparation method of blend film
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