CN103113539B

CN103113539B - Polylactic acid block copolymer, preparation method of polylactic acid block copolymer and modified polylactic acid

Info

Publication number: CN103113539B
Application number: CN201310057243.4A
Authority: CN
Inventors: 张宝; 陈学思; 李杲; 庄秀丽; 边新超; 孙敬茹
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2013-02-22
Filing date: 2013-02-22
Publication date: 2014-12-10
Anticipated expiration: 2033-02-22
Also published as: CN103113539A

Abstract

The invention discloses a polylactic acid block copolymer, a preparation method of the polylactic acid block copolymer and modified polylactic acid. The modified polylactic acid is prepared by blending 50-90 parts by weight of polylactic acid, 0.2-10 parts by weight of a polylactic acid block copolymer, 0-40 parts by weight of poly(butylene succinate) and 0-30 parts by weight of polylactic acid poly(butylene succinate). Compared with polylactic acid modified via small molecules in the prior art, firstly, all the modified components in the polylactic acid disclosed by the invention are polymers and can be branched or crosslinked, so that the stability of the modified polylactic acid is increased and the modified polylactic acid has the advantage of good compatibility; secondly, all the used modified components are degradable materials, so that the preparation cost is low and the biodegradability is good; and thirdly, the poly(butylene succinate) provides flexible chain segments for the modified polylactic acid, and the polylactic acid copolymer provides branched or cross-linked factors for the modified polylactic acid.

Description

Polylactic-acid block copolymer and preparation method thereof, polydactyl acid

Technical field

Polymeric material field of the present invention, relates in particular to polylactic-acid block copolymer and preparation method thereof, polydactyl acid.

Background technology

Plastics are absolutely necessary in people's life, but traditional plastics are general, above the even longer time of a century could be degradable, caused serious " white pollution "; Traditional plastic raw materials all derives from the Nonrenewable resources such as oil simultaneously, and the plastics industry traditional along with the exhaustion of petrochemical industry resource is also on the hazard.Therefore the eco-friendly biodegradable polymkeric substance petroleum replacing base plastic prod of Devoting Major Efforts To Developing, has become the focus that current research is developed.

Wherein, poly(lactic acid) (PLA) is very important a kind of bio-degradable plastics, that to take the lactic acid that agricultural-food corn refines be monomer, Biodegradable macromolecular material through chemosynthesis, there is nontoxic, nonirritant, good biocompatibility, intensity is high and the feature such as biodegradable and absorption, in wrapping material, biological medicine and pharmaceutical industry, have a wide range of applications.And the degradation speed of poly(lactic acid) is very fast, mix with microorganism and compound organic waste materials, can within some months, resolve into CO ₂and H ₂o.Therefore strengthen polylactic acid-based product development and application, can solve " white pollution " that perplex for a long time environment protection, and have great importance to realizing Sustainable development.

But because long-chain branch in polylactic acid molecule chain is few, shortcomings such as making it have that melt strength is low, strain hardening is not enough, toughness is poor, lack flexibility and elasticity, tear strength is low, the polymkeric substance hard and crisp for this class of poly(lactic acid) in thermoforming, melt strength is low, moulding process can only be carried out in narrow temperature range, so its application is subject to certain restrictions.And, owing to not containing the functional group with reactive behavior in the molecular chain of poly(lactic acid), be difficult for introducing long-chain branch, therefore need to find suitable PLA modified method, under the condition that does not affect the performances such as PLA biological degradability, biocompatibility, intensity, improve its shortcoming.

The people such as Louis (Macromolecules 2007,40:2327-2334) at Sn(Oct) ₂under condition for catalyzer, with R-GLYCIDOL, cause rac-Lactide ring-opening reaction, when low temperature solution polymerization, mainly there is the graft reaction of the online shape poly(lactic acid) of epoxy, when high-temperature body polymerization, the open loop simultaneously of rac-Lactide and epoxy obtains the poly(lactic acid) of certain degree of branching, this kind of method can obtain the product of high molecular, but studies have shown that and in system, take chain extension or graft reaction as main, rather than branching reaction, yet the contribution for material strain sclerosis behavior is mainly brought by branched structure, and this method can not obtain high degree of branching poly(lactic acid).

The people such as Carlson (Polymer Engineering and Science 1998, 38:311-321) in poly(lactic acid), react in extrusion with 2, 5-dimethyl-2, 5-dibutyl superoxide is initiator, by free radical hydrogen abstraction reaction, make polylactic acid molecule chain produce branching, but also may capture the hydrogen atom on tertiary carbon on PLA main chain simultaneously and cause degraded, although and this method can successfully be introduced long-chain branch, but the randomness due to free radical reaction, cause the molecular weight of end product and branching topological framework to be difficult to control, thereby affect the machine-shaping property of material.

Publication number is that the Chinese patent of CN102010583A discloses polymer long-chain branched crystalline polylactic acid material and preparation method thereof, the method by adding proton acid as catalyst in lactic acid aqueous solution, dehydration, then add diprotic acid or acid anhydrides to obtain the product of carboxy blocking, add again lewis acid catalyst polycondensation, obtain holding the poly(lactic acid) prepolymer of carboxy blocking, finally add 2-glycidyl ester and crystallization promoter, obtain long-chain branched crystalline polylactic acid, but 2-glycidyl ester is small molecules, unreacted 2-glycidyl ester can migrate to product surface, cause sample unstable.

Summary of the invention

In view of this, the technical problem to be solved in the present invention is to provide a kind of polylactic-acid block copolymer and preparation method thereof, polydactyl acid, this polydactyl acid stable performance.

The invention provides a kind of polylactic-acid block copolymer, by polylactic acid and polyethylene butanediol succinate segmented copolymer, halogen acyl halide and epoxide-functional monomer copolymerization, formed; Described halogen acyl halide is halo isobutyl carboxylic acid halides and/or halo propionyl halogen; Described epoxide-functional monomer is the epoxide-functional monomer that comprises epoxide group and acyl group.

Preferably, described halogen acyl halide is selected from one or more in bromo isobutyl acylbromide, bromo propionyl bromide, chloro isobutyryl chloride and chloro-propanoyl chloride.

Preferably, described epoxide-functional monomer is selected from one or more in compound, maleic anhydride and the dimethyl maleic anhydride of formula (I) structure:

Wherein, R ₁alkyl for H or C1～C20.

Preferably, the mol ratio of described poly(lactic acid) succinic acid-butanediol ester segmented copolymer, halogen acyl halide and epoxide-functional monomer is 1:2:(6～400).

The present invention also provides a kind of preparation method of polylactic-acid block copolymer, comprises the following steps:

A) polylactic acid and polyethylene butanediol succinate segmented copolymer is mixed with halogen acyl halide, after reaction, obtain macromole evocating agent;

B) described macromole evocating agent is mixed with epoxide-functional monomer, under the effect of catalyzer, in solvent, react, obtain polylactic-acid block copolymer;

Described halogen acyl halide is halo isobutyl carboxylic acid halides and/or halo propionyl halogen;

Described epoxide-functional monomer is the epoxide-functional monomer that comprises epoxide group and acyl group;

Described catalyzer is cuprous halide catalyst system or ferric chloride catalyst system; Described cuprous halide catalyst system forms by cuprous halide and containing N part; Described ferric chloride catalyst system by iron(ic) chloride with can form with the compound of iron coordination.

Preferably, described cuprous halide is cuprous chloride and/or cuprous bromide.

Preferably, described is the multiple tooth N part of N atomicity >=2 containing N part.

Preferably, describedly can be selected from the compound of iron coordination one or more in iminodiethanoic acid, triphenyl phosphorus and three (3,6-dioxaheptyl) amine.

Preferably, described step B carries out under the protection of rare gas element.

The present invention also provides a kind of polydactyl acid, by following component, by blend, is obtained:

Poly(lactic acid) 50～90 weight parts;

Polylactic-acid block copolymer 0.2～10 weight part described in claim 1～4 any one;

Poly butylene succinate 0～40 weight part;

Polylactic acid and polyethylene butanediol succinate segmented copolymer 0～30 weight part.

The invention provides a kind of copolymer of poly lactic acid and preparation method thereof, polydactyl acid, this polydactyl acid by the poly(lactic acid) of 50～90 weight parts, the poly butylene succinate of the polylactic-acid block copolymer of 0.2～10 weight part, 0～40 weight part and the polylactic acid and polyethylene butanediol succinate of 0～30 weight part by blend, obtain.Compare with small molecules polydactyl acid with existing, the present invention is with polylactic-acid block copolymer, poly butylene succinate and polylactic acid and polyethylene butanediol succinate polydactyl acid.First, in the present invention, all modified components are polymkeric substance, and polylactic-acid block copolymer can be uniformly distributed in polylactic resin, can or be cross-linked to form reticulated structure with poly butylene succinate and polylactic acid and polyethylene butanediol succinate segmented copolymer generation branching, the migration, the phenomenon of osmosis that owing to adding small molecules softening agent, in polylactic resin, bring have been solved, improved the stability of polydactyl acid, also made each component distribution uniform in polydactyl acid, consistency better simultaneously; Secondly, the present invention's modified component used is degradable material, and preparation cost is low, has good biological degradability; Again, poly butylene succinate provides soft segment for polydactyl acid, polylactic-acid block copolymer provides branching or crosslinked factor for polydactyl acid, when polylactic acid and polyethylene butanediol succinate segmented copolymer provides soft segment for polydactyl acid, also increased the consistency of poly butylene succinate.

Experimental result shows, the elongation at break of polydactyl acid of the present invention can be up to 280%.

Accompanying drawing explanation

Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the polylactic-acid block copolymer of preparation in the embodiment of the present invention 1;

Fig. 2 is the complex viscosity of polydactyl acid and the flow curve figure of frequency of preparation in the embodiment of the present invention 7～11 and comparative example 1;

Fig. 3 is the storage modulus of polydactyl acid and the flow curve figure of frequency of preparation in the embodiment of the present invention 7～11 and comparative example 1;

Fig. 4 is the out-of-phase modulus of polydactyl acid and the flow curve figure of frequency of preparation in the embodiment of the present invention 7～11 and comparative example 1;

Fig. 5 is the stereoscan photograph of the polydactyl acid of preparation in the embodiment of the present invention 7;

Fig. 6 is the stereoscan photograph of the polydactyl acid of preparation in the embodiment of the present invention 8;

Fig. 7 is the stereoscan photograph of the polydactyl acid of preparation in the embodiment of the present invention 9;

Fig. 8 is the stereoscan photograph of the polydactyl acid of preparation in the embodiment of the present invention 10;

Fig. 9 is the stereoscan photograph of the polydactyl acid of preparation in the embodiment of the present invention 11;

Figure 10 is the stress-strain curve diagram of the polydactyl acid of preparation in the embodiment of the present invention 7～11.

Embodiment

Wherein, described polylactic acid and polyethylene butanediol succinate segmented copolymer is polylactic acid and polyethylene butanediol succinate segmented copolymer well known to those skilled in the art, and it can be commercially available, also can be self-control, there is no special restriction.

Described halogen acyl halide is halogen acyl halide well known to those skilled in the art, there is no special restriction.In the present invention, described halo isobutyl carboxylic acid halides is preferably bromo isobutyl acylbromide and/or chloro isobutyryl chloride, is preferably bromo isobutyl acylbromide, and described halo propionyl halogen is preferably bromo propionyl bromide and/or chloro-propanoyl chloride, is preferably bromo propionyl bromide.

Described epoxide-functional monomer is the epoxide-functional monomer that comprises epoxide group and acyl group well known to those skilled in the art, there is no special restriction.In the present invention, described epoxide-functional monomer is preferably one or more in compound, maleic anhydride and the dimethyl maleic anhydride shown in formula (I), more preferably one or more in glytidyl methacrylate, Glycidyl Acrylate, maleic anhydride and dimethyl maleic anhydride.

Wherein, R is the alkyl of H or C1～C20, is preferably the alkyl of H or C1～C10, more preferably the alkyl of C1～C5.

According to the present invention, the mol ratio of described polylactic acid and polyethylene butanediol succinate segmented copolymer and halogen acyl halide there is no special restriction; The mol ratio of described polylactic acid and polyethylene butanediol succinate segmented copolymer and epoxide-functional monomer is 1:(6～400), be preferably 1:(50～200).

The number-average molecular weight of described polylactic-acid block copolymer is preferably 0.6～60,000, and it comprises poly butylene succinate block, poly(lactic acid) block and epoxide-functional monomer polymer blocks.The polymerization degree of wherein said poly butylene succinate block is preferably 8～250, and molecular weight is preferably 0.3～40,000; The polymerization degree of described poly(lactic acid) block is preferably 3～200, and molecular weight is preferably 0.3～50,000; The polymerization degree of described epoxide-functional monomer polymer blocks is preferably 3～200, and its content in polylactic-acid block copolymer is preferably 5～70wt%, more preferably 15～50wt%.

The present invention also provides a kind of preparation method of polylactic-acid block copolymer, comprises the following steps: A) polylactic acid and polyethylene butanediol succinate segmented copolymer is mixed with halogen acyl halide, obtain macromole evocating agent after reaction; B) described macromole evocating agent is mixed with epoxide-functional monomer, under the effect of catalyzer, in solvent, react, obtain polylactic-acid block copolymer; Described halogen acyl halide is halo isobutyl carboxylic acid halides and/or halo propionyl halogen; Described epoxide-functional monomer is the epoxide-functional monomer that comprises epoxide group and acyl group; Described catalyzer is cuprous halide catalyst system or ferric chloride catalyst system; Described cuprous halide catalyst system forms by cuprous halide and containing N part; Described ferric chloride catalyst system by iron(ic) chloride with can form with the compound of iron coordination.

Wherein, described polylactic acid and polyethylene butanediol succinate segmented copolymer, halogen acyl halide and epoxide-functional monomer are all same as above, do not repeat them here.

In the present invention, the Chinese patent that described polylactic acid and polyethylene butanediol succinate segmented copolymer is preferably CN102786672A according to publication number is prepared.

Described steps A is for reacting the hydroxyl of polylactic acid and polyethylene butanediol succinate end synthetic macromolecule initiator by terminal group functional method with halogen acyl halide; Under the condition that steps A described in the present invention preferably exists at the first catalyzer, react, described the first catalyzer is catalyzer well known to those skilled in the art, is preferably triethylamine; Described steps A is preferably reacted in organic solvent, more preferably methylene dichloride.

According to the present invention, the mass ratio of macromole evocating agent described in step B and epoxide-functional monomer is 30:70～90:10, is preferably 35:70～80:10, more preferably 40:70～60:10.Described cuprous halide is preferably cuprous chloride and/or cuprous bromide, and the quality of described cuprous halide or iron(ic) chloride is 0.5%～2% of macromole evocating agent quality, and more preferably 1%～1.5%.Described is the multiple tooth N part of N atomicity >=2 containing N part, is preferably selected from one or more in formula (11), formula (12) and formula (13) compound, more preferably 2,2 '-dipyridyl.

Wherein, R ₁～R ₂₀be selected from independently of one another a kind of in hydrogen and C1～C10 alkyl, be preferably hydrogen.

Described can be well known to those skilled in the artly can form with iron coordination the compound of complex compound with the compound of iron coordination, there is no special restriction, described in the present invention, can be preferably with the compound of iron coordination one or more in iminodiethanoic acid, triphenyl phosphorus and three (3,6-dioxaheptyl) amine.

Described containing N part or can be 2%～10% of macromole evocating agent quality with the quality of the compound of iron coordination, more preferably 5%～9%.

Described step B preferably reacts under the protection of rare gas element, and described rare gas element is rare gas element well known to those skilled in the art, there is no special restriction, is preferably nitrogen or argon gas in the present invention.

Macromole evocating agent described in the present invention, under the condition of protection of inert gas and catalyst action, causes the reaction of generation atom transfer free crowd and obtains polylactic-acid block copolymer.Atom transfer radical polymerization realizes by solution method, described solvent is organic solvent well known to those skilled in the art, there is no special restriction, in the present invention, be preferably toluene, dimethylbenzene, N, one or more in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), trichloromethane, methylene dichloride, tetrahydrofuran (THF), acetonitrile and dioxane.

The temperature of described atom transfer free crowd reaction is 30 ℃～120 ℃, is preferably 40 ℃～80 ℃, and the reaction times is 4～12h, is preferably 6～10h.

Take halogen acyl halide as bromo isobutyl acylbromide, and epoxide-functional monomer is that glytidyl methacrylate is example, and the route of synthesis of polylactic-acid block copolymer is as follows:

Wherein, n=8～250, are preferably 20～180; p ₁=20～600, be preferably 50～400; p ₂=20～600, be preferably 50～400; m ₁=2～200, be preferably 20～180; m ₂=2～200, be preferably 20～180.

Poly(lactic acid) 50～90 weight parts;

Polylactic-acid block copolymer 0.2～10 weight part;

Poly butylene succinate 0～40 weight part;

Wherein, described poly(lactic acid) is poly(lactic acid) well known to those skilled in the art, can be the homemade commercial polylactic resin that also can be, and there is no special restriction.The weight-average molecular weight of poly(lactic acid) described in the present invention is preferably 5～250,000, and more preferably 8～200,000.Described poly(lactic acid) is preferably 50～80 weight parts, more preferably 60～80 weight parts; Its fusing point is preferably 140 ℃～180 ℃.Poly(lactic acid) can reduce the density of epoxide-functional monomer in polylactic-acid block copolymer, can be uniformly dispersed.

Described polylactic-acid block copolymer is the polylactic-acid block copolymer of the above, and it is preferably 0.5～6 weight part, more preferably 0.5～4 weight part.In the present invention, polylactic-acid block copolymer provides branching or crosslinked factor for polydactyl acid.

Described poly butylene succinate is poly butylene succinate well known to those skilled in the art, there is no special restriction.The weight-average molecular weight of poly butylene succinate described in the present invention is preferably 1～150,000, and more preferably 5～100,000.Described poly butylene succinate is preferably 10～30 weight parts.Poly butylene succinate provides soft segment for polydactyl acid.

Described polylactic acid and polyethylene butanediol succinate segmented copolymer is polylactic acid and polyethylene butanediol succinate segmented copolymer well known to those skilled in the art, there is no special restriction.In the present invention, preferably its weight-average molecular weight is 1～190,000, more preferably 2～100,000.Described polylactic acid and polyethylene butanediol succinate segmented copolymer is preferably 2～20 weight parts.The problems such as polylactic acid and polyethylene butanediol succinate segmented copolymer, for other components in polydactyl acid provide the effect of increase-volume, has solved modified polylactic acid coblended matter skewness in the past, and consistency is poor.

According to the present invention, the method for described blend is blend method well known to those skilled in the art, there is no special restriction.In the present invention, preferably by Banbury mixer or forcing machine, carry out blend.The temperature of described blend is preferably 180 ℃～220 ℃, and more preferably 180 ℃～200 ℃, the time of described blend is preferably 3～10min, more preferably 4～8min.

Epoxide group described in the present invention in polylactic-acid block copolymer can be in Blending Processes forms reticulated structure with poly butylene succinate and polylactic acid and polyethylene butanediol succinate segmented copolymer generation branching or crosslinking reaction, and the polylactic-acid block copolymer that the present invention obtains can be uniformly distributed in polylactic resin, the migration, the phenomenon of osmosis that owing to adding small molecules softening agent, in polylactic resin, bring have been solved, improved the stability of polydactyl acid, also made each component distribution uniform in polydactyl acid, consistency better simultaneously; The present invention's modified component used is degradable material, and preparation cost is low, has good biological degradability.

According to the present invention, after described blend, preferably also carry out hot-forming.Described hot-forming method is method well known to those skilled in the art, there is no special restriction, hot-forming temperature described in the present invention is preferably 180 ℃～220 ℃, more preferably 180 ℃～220 ℃, described hot-forming pressure is preferably 5～20MPa, more preferably 8～15MPa.

In order to further illustrate the present invention, below in conjunction with embodiment, polylactic-acid block copolymer provided by the invention and preparation method thereof, polydactyl acid are described in detail.

In following examples, reagent used is commercially available.

Embodiment 1

1.1 successively add in flask than the ratio of 1:1.2 by 59g succinic acid, 54g butyleneglycol and 0.05g catalyzer metatitanic acid four butyl esters in acid alcohol, be warming up to rapidly 130 ℃, stirring reaction, collect the water generating in reaction simultaneously, when no longer including liquid and distillate to reaction, be warming up to 210 ℃, vacuumize and carry out polycondensation, after 3h, reaction finishes, and obtains poly butylene succinate.

1.2 rac-Lactides that the poly butylene succinate obtaining in 50g1.1,100g were dried mix with the sub-tin of 0.2g octoate catalyst, be warming up to 120 ℃, stir, carry out bulk polymerization, after 24h, obtain white crystalline polymkeric substance, add chloroform to dissolve, then pour in excessive ethanol and precipitate, obtain white solid, vacuum-drying, to constant weight, obtains polylactic acid and polyethylene butanediol succinate segmented copolymer.

1.3 mix the polylactic acid and polyethylene butanediol succinate segmented copolymer obtaining in 30g1.2,200ml methylene dichloride with 2ml catalyst of triethylamine, slowly drip 1.2ml bromo propionyl bromide, room temperature reaction 12h, precipitates in ethanol, vacuum-drying, obtains macromole evocating agent.

1.4 by the macromole evocating agent obtaining in 15g1.3,0.21g catalyzer cuprous chloride and 0.98g part 2,2 '-dipyridyl mixes, after three vacuum outgas-applying argon gas, sealing, with syringe, add 5g glytidyl methacrylate and 100ml solvent dioxane, be warming up to after 53 ℃ of reaction 5h cooling end reaction, with dioxane solubilizing reaction mixture, use neutral Al ₂o ₃cross post, after filtrate is concentrated, in ethanol, precipitate, vacuum-drying is to constant weight, obtain polylactic-acid block copolymer, be poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer, relative number average molecular weight is 30.0Kg/mol, and relative molecular weight is distributed as 1.83.

Utilize nucleus magnetic resonance to analyze the poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer obtaining in 1.4, obtain its hydrogen nuclear magnetic resonance spectrogram, as shown in Figure 1.A wherein, a ', b, b ', c, d, e, f, g and h are respectively the displacement of different hydro in segmented copolymer, a ' wherein, b ' is the displacement of main hydrogen in poly(lactic acid) block; A, b and c are the characterization displacement study peak in poly butylene succinate block; F(4.33ppm and 3.79ppm) be-CH ₂the displacement of OCO-group methylene radical hydrogen; G(3.21ppm) and h(2.63ppm, 2.83ppm) be the displacement of hydrogen on methyne and methylene radical in epoxide group; E is the displacement of methyl hydrogen (0.9～1.4ppm) on main chain in poly (glycidylmethacrylate--co-ethylene dimethacrylate) block.

Embodiment 2

2.1 successively add in flask than the ratio of 1:1.2 by 59g succinic acid, 54g butyleneglycol and 0.05g catalyzer metatitanic acid four butyl esters in acid alcohol, be warming up to rapidly 130 ℃, stirring reaction, collect the water generating in reaction simultaneously, when no longer including liquid and distillate to reaction, be warming up to 210 ℃, vacuumize and carry out polycondensation, after 3h, reaction finishes, and obtains poly butylene succinate.

2.2 rac-Lactides that the poly butylene succinate obtaining in 50g2.1,100g were dried mix with the sub-tin of 0.2g octoate catalyst, be warming up to 120 ℃, stir, carry out bulk polymerization, after 24h, obtain white crystalline polymkeric substance, add chloroform to dissolve, then pour in excessive ethanol and precipitate, obtain white solid, vacuum-drying, to constant weight, obtains polylactic acid and polyethylene butanediol succinate segmented copolymer.

2.3 mix the polylactic acid and polyethylene butanediol succinate segmented copolymer obtaining in 30g2.2,200ml methylene dichloride with 2ml catalyst of triethylamine, slowly drip 1.2ml bromo propionyl bromide, room temperature reaction 12h, precipitates in ethanol, vacuum-drying, obtains macromole evocating agent.

2.4 by the macromole evocating agent obtaining in 15g2.3,0.21g catalyzer cuprous chloride and 0.98g part 2,2 '-dipyridyl mixes, after three vacuum outgas-applying argon gas, sealing, with syringe, add 10g glytidyl methacrylate and 100ml solvent dioxane, be warming up to after 53 ℃ of reaction 5h cooling end reaction, with dioxane solubilizing reaction mixture, use neutral Al ₂o ₃cross post, after filtrate is concentrated, in ethanol, precipitate, vacuum-drying is to constant weight, obtain polylactic-acid block copolymer, be poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer, relative number average molecular weight is 35.0Kg/mol, and relative molecular weight is distributed as 1.82.

Embodiment 3

3.1 successively add in flask than the ratio of 1:1.2 by 59g succinic acid, 54g butyleneglycol and 0.05g catalyzer metatitanic acid four butyl esters in acid alcohol, be warming up to rapidly 130 ℃, stirring reaction, collect the water generating in reaction simultaneously, when no longer including liquid and distillate to reaction, be warming up to 210 ℃, vacuumize and carry out polycondensation, after 3h, reaction finishes, and obtains poly butylene succinate.

3.2 rac-Lactides that the poly butylene succinate obtaining in 50g3.1,100g were dried mix with the sub-tin of 0.2g octoate catalyst, be warming up to 120 ℃, stir, carry out bulk polymerization, after 24h, obtain white crystalline polymkeric substance, add chloroform to dissolve, then pour in excessive ethanol and precipitate, obtain white solid, vacuum-drying, to constant weight, obtains polylactic acid and polyethylene butanediol succinate segmented copolymer.

3.3 mix the polylactic acid and polyethylene butanediol succinate segmented copolymer obtaining in 30g3.2,200ml methylene dichloride with 2ml catalyst of triethylamine, slowly drip 1.2ml bromo propionyl bromide, room temperature reaction 12h, precipitates in ethanol, vacuum-drying, obtains macromole evocating agent.

3.4 by the macromole evocating agent obtaining in 15g3.3,0.21g catalyzer cuprous chloride and 0.98g part 2,2 '-dipyridyl mixes, after three vacuum outgas-applying argon gas, sealing, with syringe, add 20g glytidyl methacrylate and 100ml solvent dioxane, be warming up to after 53 ℃ of reaction 5h cooling end reaction, with dioxane solubilizing reaction mixture, use neutral Al ₂o ₃cross post, after filtrate is concentrated, in ethanol, precipitate, vacuum-drying is to constant weight, obtain polylactic-acid block copolymer, be poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer, relative number average molecular weight is 42.0Kg/mol, and relative molecular weight is distributed as 1.85.

Embodiment 4

4.1 successively add in flask than the ratio of 1:1.2 by 59g succinic acid, 54g butyleneglycol and 0.05g catalyzer metatitanic acid four butyl esters in acid alcohol, be warming up to rapidly 130 ℃, stirring reaction, collect the water generating in reaction simultaneously, when no longer including liquid and distillate to reaction, be warming up to 210 ℃, vacuumize and carry out polycondensation, after 3h, reaction finishes, and obtains poly butylene succinate.

4.2 rac-Lactides that the poly butylene succinate obtaining in 50g4.1,50g were dried mix with the sub-tin of 0.1g octoate catalyst, be warming up to 120 ℃, stir, carry out bulk polymerization, after 24h, obtain white crystalline polymkeric substance, add chloroform to dissolve, then pour in excessive ethanol and precipitate, obtain white solid, vacuum-drying, to constant weight, obtains polylactic acid and polyethylene butanediol succinate segmented copolymer.

4.3 mix the polylactic acid and polyethylene butanediol succinate segmented copolymer obtaining in 30g4.2,200ml methylene dichloride with 3ml catalyst of triethylamine, slowly drip 1.8ml bromo propionyl bromide, room temperature reaction 12h, precipitates in ethanol, vacuum-drying, obtains macromole evocating agent.

4.4 by the macromole evocating agent obtaining in 15g4.3,0.21g catalyzer cuprous chloride and 0.98g part 2,2 '-dipyridyl mixes, after three vacuum outgas-applying argon gas, sealing, with syringe, add 5g glytidyl methacrylate and 100ml solvent dioxane, be warming up to after 53 ℃ of reaction 5h cooling end reaction, with dioxane solubilizing reaction mixture, use neutral Al ₂o ₃cross post, after filtrate is concentrated, in ethanol, precipitate, vacuum-drying is to constant weight, obtain polylactic-acid block copolymer, be poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer, relative number average molecular weight is 20.0Kg/mol, and relative molecular weight is distributed as 1.86.

Embodiment 5

5.1 in acid alcohol, the ratio than 1: 1.2 adds in flask by 59g succinic acid, 54g butyleneglycol and 0.05g catalyzer metatitanic acid four butyl esters successively, be warming up to rapidly 130 ℃, stirring reaction, collect the water generating in reaction simultaneously, when no longer including liquid and distillate to reaction, be warming up to 210 ℃, vacuumize and carry out polycondensation, after 3h, reaction finishes, and obtains poly butylene succinate.

5.2 rac-Lactides that the poly butylene succinate obtaining in 50g5.1,50g were dried mix with the sub-tin of 0.1g octoate catalyst, be warming up to 120 ℃, stir, carry out bulk polymerization, after 24h, obtain white crystalline polymkeric substance, add chloroform to dissolve, then pour in excessive ethanol and precipitate, obtain white solid, vacuum-drying, to constant weight, obtains polylactic acid and polyethylene butanediol succinate segmented copolymer.

5.3 mix the polylactic acid and polyethylene butanediol succinate segmented copolymer obtaining in 30g5.2,200ml methylene dichloride with 3ml catalyst of triethylamine, slowly drip 1.8ml bromo propionyl bromide, room temperature reaction 12h, precipitates in ethanol, vacuum-drying, obtains macromole evocating agent.

5.4 by the macromole evocating agent obtaining in 15g5.3,0.21g catalyzer cuprous chloride and 0.98g part 2,2 '-dipyridyl mixes, after three vacuum outgas-applying argon gas, sealing, with syringe, add 10g glytidyl methacrylate and 100ml solvent dioxane, be warming up to after 53 ℃ of reaction 5h cooling end reaction, with dioxane solubilizing reaction mixture, use neutral Al ₂o ₃cross post, after filtrate is concentrated, in ethanol, precipitate, vacuum-drying is to constant weight, obtain polylactic-acid block copolymer, be poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer, relative number average molecular weight is 24.0Kg/mol, and relative molecular weight is distributed as 1.85.

Embodiment 6

6.1 successively add in flask than the ratio of 1:1.2 by 59g succinic acid, 54g butyleneglycol and 0.05g catalyzer metatitanic acid four butyl esters in acid alcohol, be warming up to rapidly 130 ℃, stirring reaction, collect the water generating in reaction simultaneously, when no longer including liquid and distillate to reaction, be warming up to 210 ℃, vacuumize and carry out polycondensation, after 3h, reaction finishes, and obtains poly butylene succinate.

6.2 rac-Lactides that the poly butylene succinate obtaining in 50g6.1,50g were dried mix with the sub-tin of 0.1g octoate catalyst, be warming up to 120 ℃, stir, carry out bulk polymerization, after 24h, obtain white crystalline polymkeric substance, add chloroform to dissolve, then pour in excessive ethanol and precipitate, obtain white solid, vacuum-drying, to constant weight, obtains polylactic acid and polyethylene butanediol succinate segmented copolymer.

6.3 mix the polylactic acid and polyethylene butanediol succinate segmented copolymer obtaining in 30g6.2,200ml methylene dichloride with 3ml catalyst of triethylamine, slowly drip 1.8ml bromo propionyl bromide, room temperature reaction 12h, precipitates in ethanol, vacuum-drying, obtains macromole evocating agent.

6.4 by the macromole evocating agent obtaining in 15g6.3,0.21g catalyzer cuprous chloride and 0.98g part 2,2 '-dipyridyl mixes, after three vacuum outgas-applying argon gas, sealing, with syringe, add 20g glytidyl methacrylate and 100ml solvent dioxane, be warming up to after 53 ℃ of reaction 5h cooling end reaction, with dioxane solubilizing reaction mixture, use neutral Al ₂o ₃cross post, after filtrate is concentrated, in ethanol, precipitate, vacuum-drying is to constant weight, obtain polylactic-acid block copolymer, be poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer, relative number average molecular weight is 29.0Kg/mol, and relative molecular weight is distributed as 1.84.

Embodiment 7

Blend sample is added in Haake Banbury mixer mixing according to the component in table 1 and weight part proportioning, 185 ℃ of mixing 5min, screw speed is 30r/min, obtain polydactyl acid, it is hot pressed on vulcanizing press to sheet material, the temperature of hot pressing is 200 ℃, and pressure is 12MPa, obtains 1.0mm sheet sheet material.The number-average molecular weight of described poly(lactic acid) is 100,000 dalton, the number-average molecular weight of poly butylene succinate is 70,000 dalton, the number-average molecular weight of polylactic acid and polyethylene butanediol succinate segmented copolymer is 40,000 dalton, and polylactic-acid block copolymer is that the number-average molecular weight of poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer is 1.2 ten thousand dalton.

The 1.0mm sheet sheet material obtaining in embodiment 7 is cut into the disk that diameter is 25mm, then utilize rotational rheometer to carry out rheology testing to it, dynamic frequency scanning is 5% in strain, under the condition that temperature is 185 ℃, carry out, dynamic frequency is scanned up to 100rad/s from 0.1rad/s, records storage modulus (G '), out-of-phase modulus (G ") and complex viscosity (η ^*) etc. parameter with the variation of frequency, as shown in Fig. 2～4, ▲ polydactyl acid for obtaining in embodiment 7.

Wherein, Fig. 2 is the complex viscosity of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 7, because Branching and cross-linking has occurred for the hydroxyl of poly butylene succinate end and epoxide group in poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer, react as shown in Figure 2, increase along with poly butylene succinate content, complex viscosity increases gradually, and due to the branched structure forming and line style poly(lactic acid) and the poly butylene succinate formation network structure of mutually tangling, the shear viscosity of polydactyl acid is all far away higher than poly(lactic acid).

Fig. 3 is the storage modulus (G ') of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 7, as shown in Figure 3, with pure line style poly(lactic acid), the storage modulus of polydactyl acid obviously increases, illustrate that polydactyl acid has longer time of relaxation and mobile slowing down than line style poly(lactic acid), in this phenomenon explanation polydactyl acid, have the appearance of long branched chain structure.

Fig. 4 is out-of-phase modulus (the flow curve figure of G ") and frequencies omega of the polydactyl acid that obtains in embodiment 7.As shown in Figure 4, in whole shearing frequency, the out-of-phase modulus of polydactyl acid is higher than the out-of-phase modulus of pure poly(lactic acid), and the out-of-phase modulus Changing Pattern of polydactyl acid is identical with the Changing Pattern of storage modulus.

The polydactyl acid obtaining in embodiment 7 is carried out to scanning electron microscope analysis, obtain the quench stereoscan photograph of section of its low temperature, as shown in Figure 5.

According to GB/T 1040-92, to obtaining polydactyl acid in embodiment 7, carry out tensile property test, obtain its stress-strain curve diagram, as shown in (A) in Figure 10.

Embodiment 8

The 1.0mm sheet sheet material obtaining in embodiment 8 is cut into the disk that diameter is 25mm, then utilize rotational rheometer to carry out rheology testing to it, dynamic frequency scanning is 5% in strain, under the condition that temperature is 185 ℃, carry out, dynamic frequency is scanned up to 100rad/s from 0.1rad/s, records storage modulus (G '), out-of-phase modulus (G ") and complex viscosity (η ^*) etc. parameter with the variation of frequency, as shown in Fig. 2～4, ▼ is the polydactyl acid obtaining in embodiment 8.

Wherein Fig. 2 is the complex viscosity of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 8.

Fig. 3 is the storage modulus (G ') of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 8.

Fig. 4 is out-of-phase modulus (the flow curve figure of G ") and frequencies omega of the polydactyl acid that obtains in embodiment 8.

The polydactyl acid obtaining in embodiment 8 is carried out to scanning electron microscope analysis, obtain the quench stereoscan photograph of section of its low temperature, as shown in Figure 6.

According to GB/T 1040-92, to obtaining polydactyl acid in embodiment 8, carry out tensile property test, obtain its stress-strain curve diagram, as shown in (B) in Figure 10.

Embodiment 9

The 1.0mm sheet sheet material obtaining in embodiment 9 is cut into the disk that diameter is 25mm, then utilize rotational rheometer to carry out rheology testing to it, dynamic frequency scanning is 5% in strain, under the condition that temperature is 185 ℃, carry out, dynamic frequency is scanned up to 100rad/s from 0.1rad/s, records storage modulus (G '), out-of-phase modulus (G ") and complex viscosity (η ^*) etc. parameter with the variation of frequency, as shown in Fig. 2～4, △ is the polydactyl acid obtaining in embodiment 9.

Wherein Fig. 2 is the complex viscosity of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 9.

Fig. 3 is the storage modulus (G ') of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 9.

Fig. 4 is out-of-phase modulus (the flow curve figure of G ") and frequencies omega of the polydactyl acid that obtains in embodiment 9.

The polydactyl acid obtaining in embodiment 9 is carried out to scanning electron microscope analysis, obtain the quench stereoscan photograph of section of its low temperature, as shown in Figure 7.

According to GB/T1040-92, to obtaining polydactyl acid in embodiment 9, carry out tensile property test, obtain its stress-strain curve diagram, as shown in (C) in Figure 10.

Embodiment 10

The 1.0mm sheet sheet material obtaining in embodiment 10 is cut into the disk that diameter is 25mm, then utilize rotational rheometer to carry out rheology testing to it, dynamic frequency scanning is 5% in strain, under the condition that temperature is 185 ℃, carry out, dynamic frequency is scanned up to 100rad/s from 0.1rad/s, records storage modulus (G '), out-of-phase modulus (G ") and complex viscosity (η ^*) etc. parameter with the variation of frequency, as shown in Fig. 2～4, ▽ is the polydactyl acid obtaining in embodiment 10.

Wherein Fig. 2 is the complex viscosity of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 10.

Fig. 3 is the storage modulus (G ') of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 10.

Fig. 4 is out-of-phase modulus (the flow curve figure of G ") and frequencies omega of the polydactyl acid that obtains in embodiment 10.

The polydactyl acid obtaining in embodiment 10 is carried out to scanning electron microscope analysis, obtain the quench stereoscan photograph of section of its low temperature, as shown in Figure 8.

According to GB/T 1040-92, to obtaining polydactyl acid in embodiment 10, carry out tensile property test, obtain its stress-strain curve diagram, as shown in (D) in Figure 10.

Embodiment 11

The 1.0mm sheet sheet material obtaining in embodiment 11 is cut into the disk that diameter is 25mm, then utilize rotational rheometer to carry out rheology testing to it, dynamic frequency scanning is 5% in strain, under the condition that temperature is 185 ℃, carry out, dynamic frequency is scanned up to 100rad/s from 0.1rad/s, records storage modulus (G '), out-of-phase modulus (G ") and complex viscosity (η ^*) etc. parameter with the variation of frequency, as shown in Fig. 2～4, zero polydactyl acid for obtaining in embodiment 11.

Wherein Fig. 2 is the complex viscosity of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 11.

Fig. 3 is the storage modulus (G ') of polydactyl acid and the flow curve figure of frequencies omega obtaining in embodiment 11.

Fig. 4 is out-of-phase modulus (the flow curve figure of G ") and frequencies omega of the polydactyl acid that obtains in embodiment 11.

The polydactyl acid obtaining in embodiment 11 is carried out to scanning electron microscope analysis, obtain the quench stereoscan photograph of section of its low temperature, as shown in Figure 9.According to GB/T 1040-92, to obtaining polydactyl acid in embodiment 11, carry out tensile property test, obtain its stress-strain curve diagram, as shown in (E) in Figure 10.

Embodiment 12

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 30%.

Embodiment 13

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 80%.

Embodiment 14

Blend sample is added in Haake Banbury mixer mixing according to the component in table 1 and weight part proportioning, 185 ℃ of mixing 5min, screw speed is 30r/min, obtain polydactyl acid, it is hot pressed on vulcanizing press to sheet material, the temperature of hot pressing is 200 ℃, and pressure is 12MPa, obtains 1.0mm sheet sheet material.The number-average molecular weight of described poly(lactic acid) is 150,000 dalton, the number-average molecular weight of poly butylene succinate is 70,000 dalton, the number-average molecular weight of polylactic acid and polyethylene butanediol succinate segmented copolymer is 40,000 dalton, and polylactic-acid block copolymer is that the number-average molecular weight of poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer is 1.2 ten thousand dalton.

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 40%.

Embodiment 15

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 84%.

Embodiment 16

Embodiment 17

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 107%.

Embodiment 18

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 45%.

Embodiment 19

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 110%.

Embodiment 20

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 56%.

Embodiment 21

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 180%.

Embodiment 22

Embodiment 23

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 250%.

Embodiment 24

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 26%.

Embodiment 25

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 54%.

Embodiment 26

Blend sample is added in Haake Banbury mixer mixing according to the component in table 1 and weight part proportioning, 185 ℃ of mixing 5min, screw speed is 30r/min, obtain polydactyl acid, it is hot pressed on vulcanizing press to sheet material, the temperature of hot pressing is 200 ℃, and pressure is 12MPa, obtains 1.0mm sheet sheet material.The number-average molecular weight of described poly(lactic acid) is 100,000 dalton, the number-average molecular weight of poly butylene succinate is 70,000 dalton, the number-average molecular weight of polylactic acid and polyethylene butanediol succinate segmented copolymer is 40,000 dalton, and polylactic-acid block copolymer is that the number-average molecular weight of poly butylene succinate-poly(lactic acid)-poly (glycidylmethacrylate--co-ethylene dimethacrylate) segmented copolymer is 2.4 ten thousand dalton.

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 32%.

Embodiment 27

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 60%.

Embodiment 28

Embodiment 29

Embodiment 30

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 42%.

Embodiment 31

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 105%.

Embodiment 32

Embodiment 33

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 205%.

Embodiment 34

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 115%.

Embodiment 35

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 280%.

Comparative example 1

Blend sample is added in Haake Banbury mixer mixing according to the component in table 1 and weight part proportioning, 180 ℃ of mixing 5min, screw speed is 30r/min, obtain polydactyl acid, it is hot pressed on vulcanizing press to sheet material, the temperature of hot pressing is 200 ℃, and pressure is 12MPa, obtains 1.0mm sheet sheet material.The number-average molecular weight of described poly(lactic acid) is 100,000 dalton.

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 4.2%.

The 1.0mm sheet sheet material obtaining in comparative example 1 is cut into the disk that diameter is 25mm, then utilize rotational rheometer to carry out rheology testing to it, dynamic frequency scanning is 5% in strain, under the condition that temperature is 185 ℃, carry out, dynamic frequency is scanned up to 100rad/s from 0.1rad/s, records storage modulus (G '), out-of-phase modulus (G ") and complex viscosity (η ^*) etc. parameter with the variation of frequency, as shown in Fig. 2～4, ■ is the polydactyl acid obtaining in comparative example 1.

Wherein, Fig. 2 is the complex viscosity of polydactyl acid and the flow curve figure of frequencies omega obtaining in comparative example 1.

Fig. 3 is the storage modulus (G ') of polydactyl acid and the flow curve figure of frequencies omega obtaining in comparative example 1.

Fig. 4 is out-of-phase modulus (the flow curve figure of G ") and frequencies omega of the polydactyl acid that obtains in comparative example 1.

Comparative example 2

Blend sample is added in Haake Banbury mixer mixing according to the component in table 1 and weight part proportioning, 180 ℃ of mixing 5min, screw speed is 30r/min, obtain polydactyl acid, it is hot pressed on vulcanizing press to sheet material, the temperature of hot pressing is 200 ℃, and pressure is 12MPa, obtains 1.0mm sheet sheet material.The number-average molecular weight of described poly(lactic acid) is 100,000 dalton, and the number-average molecular weight of poly butylene succinate is 70,000 dalton.

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 9%.

Comparative example 3

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 20%.

Comparative example 4

Blend sample is added in Haake Banbury mixer mixing according to the component in table 1 and weight part proportioning, 180 ℃ of mixing 5min, screw speed is 30r/min, obtain polydactyl acid, it is hot pressed on vulcanizing press to sheet material, the temperature of hot pressing is 200 ℃, and pressure is 12MPa, obtains 1.0mm sheet sheet material.The number-average molecular weight of described poly(lactic acid) is 150,000 dalton, and the number-average molecular weight of poly butylene succinate is 70,000 dalton.

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 7%.

Comparative example 5

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 15%.

Comparative example 6

Blend sample is added in Haake Banbury mixer mixing according to the component in table 1 and weight part proportioning, 180 ℃ of mixing 5min, screw speed is 30r/min, obtain polydactyl acid, it is hot pressed on vulcanizing press to sheet material, the temperature of hot pressing is 200 ℃, and pressure is 12MPa, obtains 1.0mm sheet sheet material.The number-average molecular weight of described poly(lactic acid) is 100,000 dalton, and the number-average molecular weight of poly butylene succinate is 70,000 dalton, and the number-average molecular weight of polylactic acid and polyethylene butanediol succinate is 40,000 dalton.

Sheet sheet material is cut into dumbbell shape batten, the long 20mm of its venturi portion, wide 4mm, carries out tensile property test, and rate of extension is 20mm/min, and obtaining its elongation at break is 18%.

Comparative example 7

Comparative example 8

Blend sample is added in Haake Banbury mixer mixing according to the component in table 1 and weight part proportioning, 180 ℃ of mixing 5min, screw speed is 30r/min, obtain polydactyl acid, it is hot pressed on vulcanizing press to sheet material, the temperature of hot pressing is 200 ℃, and pressure is 12MPa, obtains 1.0mm sheet sheet material.The number-average molecular weight of described poly(lactic acid) is 150,000 dalton, and the number-average molecular weight of poly butylene succinate is 70,000 dalton, and the number-average molecular weight of polylactic acid and polyethylene butanediol succinate is 40,000 dalton.

Comparative example 9

The component that table 1 embodiment 7～36 and comparative example 1～10 are added and each ingredients weight parts proportioning

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

1. a polylactic-acid block copolymer, is characterized in that, by polylactic acid and polyethylene butanediol succinate segmented copolymer, halogen acyl halide and epoxide-functional monomer copolymerization, is formed; Described halogen acyl halide is halo isobutyl carboxylic acid halides and/or halo propionyl halogen; Described epoxide-functional monomer is the epoxide-functional monomer that comprises epoxide group and acyl group;

The number-average molecular weight of described polylactic-acid block copolymer is 0.6～60,000.

2. polylactic-acid block copolymer according to claim 1, is characterized in that, described halogen acyl halide is selected from one or more in bromo isobutyl acylbromide, bromo propionyl bromide, chloro isobutyryl chloride and chloro-propanoyl chloride.

3. polylactic-acid block copolymer according to claim 1, is characterized in that, described epoxide-functional monomer is selected from one or more in compound, maleic anhydride and the dimethyl maleic anhydride of formula (I) structure:

Wherein, R ₁alkyl for H or C1～C20.

4. polylactic-acid block copolymer according to claim 1, is characterized in that, the mol ratio of described poly(lactic acid) succinic acid-butanediol ester segmented copolymer, halogen acyl halide and epoxide-functional monomer is 1:2:(6～400).

5. a preparation method for polylactic-acid block copolymer, is characterized in that, comprises the following steps:

6. preparation method according to claim 5, is characterized in that, described cuprous halide is cuprous chloride and/or cuprous bromide.

7. preparation method according to claim 5, is characterized in that, described is the multiple tooth N part of N atomicity >=2 containing N part.

8. preparation method according to claim 5, is characterized in that, describedly can be selected from the compound of iron coordination one or more in iminodiethanoic acid, triphenyl phosphorus and three (3,6-dioxaheptyl) amine.

9. preparation method according to claim 5, is characterized in that, described step B carries out under the protection of rare gas element.

10. a polydactyl acid, is characterized in that, by following component, by blend, is obtained: