CN103788599A - Polylactic acid-polyester composite material and preparation method thereof - Google Patents
Polylactic acid-polyester composite material and preparation method thereof Download PDFInfo
- Publication number
- CN103788599A CN103788599A CN201210420781.0A CN201210420781A CN103788599A CN 103788599 A CN103788599 A CN 103788599A CN 201210420781 A CN201210420781 A CN 201210420781A CN 103788599 A CN103788599 A CN 103788599A
- Authority
- CN
- China
- Prior art keywords
- integer
- weight
- poly
- formula
- lactic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C*C(*1[C@]2(C)C1)C=C1CC2=CCC1 Chemical compound C*C(*1[C@]2(C)C1)C=C1CC2=CCC1 0.000 description 5
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a polylactic acid-polyester composite material. The composite material contains polylactic acid, linear and random aliphatic aromatic copolyester, triblock copolyester and an organic peroxide. The invention also relates to a preparation method of the polylactic acid-polyester composite material. The method comprises the following steps: mixing polylactic acid, the aliphatic aromatic copolyester, the triblock copolyester and the organic peroxide, and carrying out extruding granulation of the above obtained mixture. The polylactic acid-polyester composite material has excellent comprehensive mechanical performances and an excellent biological degradability.
Description
Technical field
The present invention relates to a kind of poly(lactic acid)-polyester composite, the preparation method of this poly(lactic acid)-polyester composite, and poly(lactic acid)-polyester composite of being prepared by the method.
Background technology
Poly(lactic acid) is as the Biodegradable material that comes from bio-based, because it has broken away from unique dependency of petroleum resources, and product can be degradable under the effect of microorganism after use, final product is carbonic acid gas and water, return the natural track of Life Cycles, its significant low-carbon (LC) load property, biocompatibility, biodegradation character and good mechanical property and use properties, other any material all cannot be equal to it at present.But the defects such as the fragility that poly-lactic acid material self shows because of higher second-order transition temperature (about 50-60 ℃) and the poor heat resistance that causes because self softening temperature is low have greatly limited the application of poly(lactic acid).Therefore, investigators are devoted to the toughness reinforcing and thermotolerance of poly(lactic acid) to carry out a large amount of research one after another both at home and abroad.
It is mainly to be undertaken by the mode of copolymerization and blend that poly(lactic acid) is carried out to toughening modifying.Modification by copolymerization complex process, the production cycle is long, and cost is high, and more difficult enforcement is difficult to industrialization and produces continuously.Therefore, adopt the mode of blend, on existing apparatus, poly(lactic acid) is carried out to toughening modifying owing to easily implementing to become the preferred version of toughening modifying.For toughening modifying, best toughner is exactly the elastomer material of rubber-like, as the MBS using in CN101875763A, the ethylene copolymer using in CN101495568A, US20100112357 and US20060263394 or the olefin(e) compound with epoxy-functional are as impact modifier and plasticized modifier etc., but this class material self is non-degradable material, after mixing with poly(lactic acid), can affect the biodegradation character of material, lose on the contrary the original environmental protection superiority that differs from other material of poly(lactic acid).Therefore, using Biodegradable material is the optimal selection to poly(lactic acid) toughening modifying as polylactic acid toughening modifier.
In CN1392891A and US20020198332, mention poly(lactic acid) is mixed with aliphatic polyester, add the segmented copolymer of the two as expanding material simultaneously, can improve spinning and the tensile property of poly(lactic acid).In US20020151618 and US20040092672, mention the tertiary mixture of poly(lactic acid) and PHA and aliphatic polyester composition, can prepare soft film material.In US20070203291, CN1531573A and CN1489616A, all mention and use the tertiary mixture of poly(lactic acid) and other degradable polyester or copolyesters composition to there is extraordinary tear resistance etc.In CN101024696A, mention preparation poly(lactic acid) and aliphatic poly esterdiol and under the existence of chainextender vulcabond, carry out chain extending reaction, prepare block polymer, can obtain good toughness, tensile strength is large and tension set is high poly-lactic acid material.The toughening modifying effect of above-mentioned blend toughening effect aspect anti-impact and tensile property is still very limited, its tension set of material take poly(lactic acid) as external phase is difficult to meet or exceed 300%, and the breach resistance to impact shock of material does not have clear improvement.In addition, carry out modification meeting with vulcabond as chainextender and bring certain toxicity to material.
Summary of the invention
The object of the invention is in order to overcome the toughening effect aspect erosion-resisting characteristics and tensile property that existing poly(lactic acid) toughening modifying method exists limited, or after modification, can bring toxicity or the biodegradability defect with respect to the obvious reduction of poly(lactic acid), a kind of poly(lactic acid)-polyester composite and preparation method thereof is provided.
The invention provides a kind of poly(lactic acid)-polyester composite, this matrix material contains poly(lactic acid), linear random aliphatics aromatic copolyester, tri-block copolyester and organo-peroxide, wherein, the structural formula of described tri-block copolyester as shown in Equation 1:
Formula 1
Wherein, the integer that p is 5-200, the integer that q is 5-200, M comprises the structural unit as shown in following formula 2 and formula 3,
Formula 2
Formula 3
Wherein, Ar is the group with phenyl ring, naphthalene nucleus or anthracene nucleus; M is the integer of 1-20, the integer that n is 1-16, the integer that t is 1-20;
The mol ratio of the structural unit shown in formula 2 and formula 3 is 1:0.1-10, and the weight-average molecular weight of M section is 6000-600,000, and the weight-average molecular weight of described tri-block copolyester is 10,000-1,000,000;
The random aliphatics aromatic copolyester of described linearity comprises as shown in the formula the structural unit shown in 4:
Wherein, a is the integer of 2-10, b is the integer of 0-8, the integer that c is 2-10, and a, b and c are identical or different, d is the integer of 1-10, e is the integer of 1-10, and the weight-average molecular weight of the random aliphatics aromatic copolyester of described linearity is 100,000-600,000, molecular weight distribution coefficient is 1.2-3.
The present invention also provides the preparation method of described poly(lactic acid)-polyester composite, the method comprises: poly(lactic acid), linear random aliphatics aromatic copolyester, tri-block copolyester and organo-peroxide are mixed, and the mixture obtaining is carried out to extruding pelletization.
The present invention also provides poly(lactic acid)-polyester composite of being prepared by aforesaid method.
In described poly(lactic acid)-polyester composite provided by the invention, organo-peroxide and described tri-block copolyester not only can strengthen the consistency of poly(lactic acid) and the mixed system of linear random aliphatics aromatic copolyester, but also can play the effect of chain extension increase-volume, thereby make described poly(lactic acid)-polyester composite comprehensive mechanical property better, particularly in the toughness aspect erosion-resisting characteristics and tensile property with improvement.
And each component in described poly(lactic acid)-polyester composite of the present invention is all nontoxic with biodegradable.Therefore, described poly(lactic acid)-polyester composite is eco-friendly, has good biodegradability.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 represents the nmr spectrum of the tri-block copolyester using in embodiment 1.
Embodiment
The invention provides a kind of poly(lactic acid)-polyester composite, this matrix material contains poly(lactic acid), linear random aliphatics aromatic copolyester, tri-block copolyester and organo-peroxide, wherein, the structural formula of described tri-block copolyester as shown in Equation 1:
Formula 1
Wherein, the integer that p is 5-200, the integer that q is 5-200, M comprises the structural unit as shown in following formula 2 and formula 3,
Formula 2
Formula 3
Wherein, Ar is the group with phenyl ring, naphthalene nucleus or anthracene nucleus; M is the integer of 1-20, the integer that n is 1-16, the integer that t is 1-20;
The mol ratio of the structural unit shown in formula 2 and formula 3 is 1:0.1-10, and the weight-average molecular weight of M section is 6000-600,000, and the weight-average molecular weight of described tri-block copolyester is 10,000-1,000,000;
The random aliphatics aromatic copolyester of described linearity comprises as shown in the formula the structural unit shown in 4:
Wherein, a is the integer of 2-10, b is the integer of 0-8, the integer that c is 2-10, and a, b and c are identical or different, d is the integer of 1-10, e is the integer of 1-10, and the weight-average molecular weight of the random aliphatics aromatic copolyester of described linearity is 100,000-600,000, molecular weight distribution coefficient is 1.2-3.
In the present invention, the weight-average molecular weight of polymkeric substance and molecular weight distribution coefficient record according to gel permeation chromatography (GPC).
In the present invention, in order to obtain the poly(lactic acid)-polyester composite with improved toughness and good biodegradability, be mainly by adding described tri-block copolyester and the described organo-peroxide that can play chain extension increase-volume to realize in the compound system to poly(lactic acid) and linear random aliphatics aromatic copolyester.As long as owing to adding described tri-block copolyester and described organo-peroxide, their chain extension compatibilization will be very obvious, therefore, in described poly(lactic acid)-polyester composite, described poly(lactic acid), there is no particular limitation for random aliphatics aromatic copolyester, described tri-block copolyester and the described organo-peroxide content of described linearity.In the preferred case, in order to make described poly(lactic acid)-polyester composite there is toughness and the comprehensive mechanical property of further improvement, take the gross weight of described poly(lactic acid)-polyester composite as benchmark, the content of described poly(lactic acid) is 10-90 % by weight, the content of the random aliphatics aromatic copolyester of described linearity is 5-70 % by weight, the content of described tri-block copolyester is 1-20 % by weight, and the content of described organo-peroxide is 0.01-1 % by weight.More preferably, take the gross weight of described poly(lactic acid)-polyester composite as benchmark, the content of described poly(lactic acid) is 50-70 % by weight; The content of the random aliphatics aromatic copolyester of described linearity is 20-45 % by weight; The content of described tri-block copolyester is 5-18 % by weight; The content of described organo-peroxide is 0.05-0.2 % by weight.
In the present invention, the weight-average molecular weight of described tri-block copolyester is preferably 80,000-600, and 000.
As described tri-block copolyester, in formula 1, p is preferably the integer of 10-100, and q is preferably the integer of 10-100; The weight-average molecular weight of M section is preferably 60,000-120, and 000.
As described tri-block copolyester, in formula 2, m is preferably the integer of 2-10, and n is preferably the integer of 2-8.
As described tri-block copolyester, in formula 3, t is preferably the integer of 2-10.
As described tri-block copolyester, the mol ratio of the structural unit shown in formula 2 and formula 3 is preferably 1:0.5-2.
As described tri-block copolyester, in formula 3, Ar is preferably following aryl:
Wherein, R
1, R
2, R
3, R
4, R
5and R
6be alkyl, F, the Cl ,-NO of hydrogen, C1-C4 independently of one another
2,-CN or-OR
7, wherein, R
7for the alkyl of C1-C4.
In most preferred situation, Ar is
wherein, R
1and R
2same as above.
As described tri-block copolyester, in formula 1, M can be at least one in alternating copolymerization segment, block copolymerization segment and random copolymerization segment.
Concrete, in the time that M is alternating copolymerization segment, M can be as shown in the formula shown in 4:
Formula 4
Wherein, m, n, t and Ar are same as above, and z can be the integer of 5-200, is preferably the integer of 10-100.
In the time that M is block copolymerization segment, M can be as shown in the formula shown in 5:
Formula 5
Wherein, m, n, t and Ar are same as above, and x can be the integer of 2-100, is preferably the integer of 3-30; Y can be the integer of 2-100, is preferably the integer of 3-30; W can be the integer of 5-200, is preferably the integer of 10-100.
In the time that M is random copolymerization segment, M has multiple as shown in the formula structural unit shown in 6,
Formula 6
Wherein, m, n, t and Ar are same as above, u and/or v difference in the structural unit shown in any two formulas 6 of M, and u and v can be the integer of 2-100, are preferably the integer of 3-30.
Described tri-block copolyester can prepare according to conventional method.In the preferred case, described tri-block copolyester can be according to disclosed method preparation in CN102443145A.Particularly, the preparation method of described tri-block copolyester can comprise: under the existence of organo-tin compound, under esterification condition, under inert atmosphere, straight chain type aliphatics aromatic copolyester is contacted with rac-Lactide, described straight chain type aliphatics aromatic copolyester comprises the structural unit as shown in following formula 2 and formula 3
Formula 2
Formula 3
Wherein, the integer that m is 1-20, is preferably the integer of 2-10; N is the integer of 1-16, is preferably the integer of 2-8; T is the integer of 1-20, is preferably the integer of 2-10; The mol ratio of the structural unit shown in formula 2 and formula 3 is 1:0.1-10, is preferably 1:0.5-2; The weight-average molecular weight of described straight chain type aliphatics aromatic copolyester can be 6000-600,000, be preferably 60,000-120,000;
In formula 3, Ar is the group with phenyl ring, naphthalene nucleus or anthracene nucleus, and under preferable case, Ar is following aryl:
Wherein, R
1, R
2, R
3, R
4, R
5and R
6be alkyl, F, the Cl ,-NO of hydrogen, C1-C4 independently of one another
2,-CN or-OR
7, wherein, R
7for the alkyl of C1-C4; In most preferred situation, Ar is
wherein, R
1and R
2same as above.
Described straight chain type aliphatics aromatic copolyester can be at least one in alternating copolymer, segmented copolymer and random copolymers, is preferably alternating copolymer and/or segmented copolymer.Described straight chain type aliphatics aromatic copolyester can be commercially available (for example can purchased from BASF Aktiengesellschaft), also can make according to conventional method, the preparation method of this straight chain type aliphatics aromatic copolyester can comprise: in the existence of polycondensation catalyst, make aromatic dibasic acid, binary acid and aliphatic dihydric alcohol under reduced pressure, at 160-280 ℃, polycondensation occurs, described polycondensation catalyst for example can be for being selected from least one in tetrabutyl titanate, tetrabutyl titanate, antimony acetate and antimonous oxide.
In the preparation method of above-mentioned tri-block copolyester, with respect to the rac-Lactide of 100 weight parts, the consumption of described straight chain type aliphatics aromatic copolyester can be 5-100 weight part, is preferably 10-40 weight part; The consumption of described organo-tin compound can be 0.1-10 weight part, is preferably 0.2-2 weight part.
In the preparation method of above-mentioned tri-block copolyester, described esterification condition can comprise: temperature of reaction is 130-190 ℃, is preferably 150-190 ℃, more preferably 170-190 ℃; Reaction times is 1-10 hour, is preferably 2-6 hour.
In the preparation method of above-mentioned tri-block copolyester, described esterification can realize under normal pressure, but, under pressurized conditions, can also further improve speed of response.
In the preparation method of above-mentioned tri-block copolyester, described inert atmosphere refers to the environment being formed by the gas not reacting with described straight chain type aliphatics aromatic series and rac-Lactide, and this gas can be nitrogen and conventional rare gas element.
Described organo-tin compound can be the organo-tin compound of the catalyzer as esterification of various routines, and under preferable case, described organo-tin compound is the sub-tin of stannous octoate and/or trifluoromethayl sulfonic acid.
Described rac-Lactide can be at least one in levorotatory lactide (LLA), dextrorotation rac-Lactide (DLA) and Study of Meso-Lactide (DLLA), and in most preferred situation, described rac-Lactide is LLA.
In the preparation method of above-mentioned tri-block copolyester, the method of isolating tri-block copolyester of the present invention from esterification in the product obtaining can comprise: the product obtaining after esterification is mixed with chloroform, and the mixture obtaining is precipitated in methyl alcohol and/or ethanol, then by drying precipitate.
In described poly(lactic acid)-polyester composite of the present invention, the weight-average molecular weight of described poly(lactic acid) can be 80,000-200,000, be preferably 100,000-150,000.
Described poly(lactic acid) can be the poly(lactic acid) of various routines, for example, can be PLLA (PLLA) and/or D-poly(lactic acid) (PDLA).In the preferred case, the PLLA that described poly(lactic acid) contains 50-100 % by weight and the PDLA of 0-50 % by weight.
As the random aliphatics aromatic copolyester of described linearity, in formula 4, a is preferably the integer of 2-4, and b is preferably the integer of 2-4, and c is preferably the integer of 2-4, and d is preferably the integer of 1-3, and e is preferably the integer of 1-2.
As the random aliphatics aromatic copolyester of described linearity, its weight-average molecular weight is preferably 100,000-300, and 000, molecular weight distribution coefficient is preferably 1.5-2.5.
The fusing point of the random aliphatics aromatic copolyester of described linearity can be 20-185 ℃.
The second-order transition temperature (Tg) of the random aliphatics aromatic copolyester of described linearity can be-55 ℃ to-7 ℃.In the present invention, the second-order transition temperature of polymkeric substance detects and obtains according to differential scanning calorimeter (DSC) assay method.
The random aliphatics aromatic copolyester of described linearity can prepare according to conventional method.In the preferred case, the random aliphatics aromatic copolyester of described linearity can be according to disclosed method preparation in CN1807485A.Particularly, the preparation method of the random aliphatics aromatic copolyester of described linearity can comprise the following steps:
(1) will add and in reactor, carry out transesterification reaction and/or esterification with lower unit and nonessential catalyst component Cat1: (a) ester of aromatic acid, aromatic acid, aromatic dicarboxylic anhydride or their arbitrary combination; (b) aliphatic dihydroxy alcohol, alicyclic dibasic alcohol or their arbitrary combination; And (c) aliphatic dibasic acid, alicyclic diprotic acid, their ester, their acid anhydrides or their arbitrary combination, wherein, can be (a) 5:95 to 75:25 with mol ratio (c);
(2), under vacuum condition, the reaction product that step (1) is obtained is carried out pre-polymerization; And
(3) in the prepolymer product obtaining to step (2), add catalyst component Cat2, carry out vacuum polycondensation, thereby make linear random aliphatics aromatic copolyester;
Wherein, described catalyst component Cat1 is the compound that is selected from metal titanium, the compound of antimony, the compound of zinc and their arbitrary combination;
Described catalyst component Cat2 is compound and the arbitrary combination thereof that is selected from metal Ln, and wherein said metal Ln is at least one in lanthanon, scandium and yttrium.
In step (1), can first aromatic monomer (a) be reacted with dibasic alcohol monomer (b), and then add aliphatic monomer (c); Also can first aliphatic monomer (c) be reacted with dibasic alcohol monomer (b), and then add aromatic monomer (a).Preferably, in step (1), first add reactor to react described catalyst component Cat1, monomer (a) and monomer (b); And then add monomer (c) to react.So more be conducive to fully carrying out of transesterification reaction and esterification.
In a kind of embodiment, monomer (a), monomer (b) and described catalyst component Cat1 first add reactor, preferably at 150-230 ℃, carry out the first step esterification or transesterification reaction, 90 % by weight that reach theoretical amount wait the small molecules cut receiving are when above, add monomer (c), preferably at 160-250 ℃, carry out second step esterification or transesterification reaction, 90 % by weight that reach theoretical amount wait the small molecules cut receiving are carried out follow-up pre-collecting process when above.
Above-mentioned two step esterifications or transesterification reaction can be carried out under normal pressure, vacuum and pressurized state, preferably under normal pressure, carry out.
The pre-collecting process of step (2) is preferably that 200-600Pa(is preferably 200-300Pa at 190-250 ℃, vacuum tightness) condition under carry out.The time of prepolymerization reaction can be 1-3 hour, is preferably 1-2 hour.In the present invention, vacuum tightness represents by absolute pressure.
In step (3), the temperature of polycondensation is preferably 200-300 ℃, more preferably 220-280 ℃.Described polycondensation is preferably carried out under vacuum tightness is the condition of (more preferably below 200Pa) below 300Pa.The time of described polycondensation can be 3-8 hour.
In the preparation method of the random aliphatics aromatic copolyester of above-mentioned linearity, step (1) to (3) can be carried out in same reactor.
Monomer (a) is preferably 5:95 to 65:35, more preferably 35:65 to 60:40 with the mol ratio of monomer (c).The mol ratio of the mole number sum of monomer (a) and monomer (c) and monomer (b) is preferably 1:1-3, more preferably 1:1-2, and more preferably 1:1.1-1.5, is further preferably 1:1.2-1.4.The ratio of the mole number sum of the mole number sum of described catalyst component Cat1 and described catalyst component Cat2 and monomer (a) and monomer (c) is 1:500-10,000, be preferably 1000-3000.
Monomer (a) is preferably to phenyl diprotic acid, ester to phenyl diprotic acid with at least one in phenyl dibasic acid anhydride, more preferably terephthalic acid and/or dimethyl terephthalate (DMT).
Monomer (b) is preferably the aliphatic dihydroxy alcohol of C2-C6 and/or the alicyclic dibasic alcohol of C5-C10, is preferably at least one in BDO, 1,3-PD and ethylene glycol.
Monomer (c) is preferably the aliphatic dibasic acid of C3-C10, the alicyclic diprotic acid of C3-C10, their ester, their acid anhydrides and their arbitrary combination, is preferably at least one in hexanodioic acid, sebacic acid and succinic acid.
Described catalyst component Cat1 is preferably oxide compound, the M (OR of M
1)
fand M (OOCR
2)
gin one or more, wherein, M is titanium, antimony or zinc, f and g are the valence state of M independently of one another, R
1for C
1-C
10alkyl, R
2for C
1-C
30alkyl; More preferably titan-alkoxide (Ti (OR
1)
f), at least one in oxide compound and the titanyl compound of the oxide compound of zinc acetate, zinc, antimony; More preferably at least one in tetrabutyl titanate, titanium isopropoxide, titanium dioxide and zinc acetate.
Described catalyst component Cat2 is preferably Ln (R
3)
3compound, wherein, R
3for being selected from halogen, alkoxyl group, aryloxy, acetylacetone based and R
4at least one in COO-group, R
4for C
1-C
30alkyl; Ln is at least one in lanthanum, cerium, praseodymium, neodymium, terbium, ytterbium, dysprosium, samarium and scandium, is preferably at least one in lanthanum, cerium, praseodymium, neodymium and scandium.
The mol ratio of described catalyst component Cat1 and described catalyst component Cat2 can be 0:100 to 95:5, is preferably 1:3 to 3:1, more preferably 2:3 to 3:2.
In described poly(lactic acid)-polyester composite of the present invention, described organo-peroxide can be the organo-peroxide that can play the various routines of chain extension compatibilization.Under preferable case, described organo-peroxide is the operational condition half-life (t in extruding pelletization process
1/2) be the organo-peroxide of 0.2-10 minute, further preferred, described organo-peroxide is dicumyl peroxide, 2,5-dimethyl-2, at least one in two (tert-butyl peroxide) hexanes of 5-, two (t-butyl peroxy sec.-propyl) benzene, dibenzoyl peroxide, lauroyl peroxide and tert-butyl hydroperoxide isobutyrate.
In the present invention, described poly(lactic acid)-polyester composite can also contain other additives, for example, can also contain slipping agent and/or oxidation inhibitor.Described slipping agent can be conventionally used as for this area the material of slipping agent, for example can be for the aminocompound take lipid acid as substrate, as erucicamide, amine hydroxybenzene, stearic amide fourth.Described oxidation inhibitor can be conventionally used as for this area the material of oxidation inhibitor, it can be for example hindered phenol type antioxidant, β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic esters as two in triglycol (being called for short oxidation inhibitor 245) and/or 3,5-di-t-butyl-4 hydroxy-phenylpropionic acid octadecanol esters (abbreviation antioxidant 1076).In described poly(lactic acid)-polyester composite, take the gross weight of described poly(lactic acid)-polyester composite as benchmark, the content of described slipping agent can be 0-0.2 % by weight, is preferably 0.001-0.2 % by weight; The content of described oxidation inhibitor can be 0-0.2 % by weight, is preferably 0.001-0.2 % by weight.
The present invention also provides a kind of method of preparing poly(lactic acid)-polyester composite, the method comprises: poly(lactic acid), linear random aliphatics aromatic copolyester, tri-block copolyester and organo-peroxide are mixed, and the mixture obtaining is carried out to extruding pelletization.
Random aliphatics aromatic copolyester, described tri-block copolyester and the described organo-peroxide of described poly(lactic acid), described linearity all with describe above identical.
Described poly(lactic acid), the aliphatics aromatic copolyester that described linearity is random, the equal consumption of described tri-block copolyester and described organo-peroxide preferably makes the described poly(lactic acid) that contains 10-90 % by weight (being preferably 50-70 % by weight) in the poly(lactic acid)-polyester composite of final preparation, the random aliphatics aromatic copolyester of described linearity of 5-70 % by weight (being preferably 20-45 % by weight), the described organo-peroxide of the described tri-block copolyester of 1-20 % by weight (being preferably 5-18 % by weight) and 0.01-1 % by weight (being preferably 0.05-0.2 % by weight).
In the process that poly(lactic acid), linear random aliphatics aromatic copolyester, tri-block copolyester and organo-peroxide are mixed, preferably first described organo-peroxide is dissolved in organic solution, obtain the organic solution of organo-peroxide, then the organic solution of this organo-peroxide is mixed with other components.
Mixing with other components with the form of organic solution at described organo-peroxide, described method preferably also comprises the mixture obtaining in described mixing process is dried.The described dry 1-2 days that for example can carry out at 50-60 ℃ in loft drier.
Described extruding pelletization process can be implemented according to conventional extruding pelletization method.Under preferable case, described extruding pelletization process is carried out at 80-180 ℃ in twin screw extruder.Further preferably, described twin screw extruder comprises four temperature sections, and the temperature of each section is followed successively by 100-105 ℃, 165-170 ℃, 165-170 ℃ and 160-165 ℃ from opening for feed to extrusion.
In the present invention, the described method of preparing poly(lactic acid)-polyester composite can also comprise: in the process that poly(lactic acid), linear random aliphatics aromatic copolyester, tri-block copolyester and organo-peroxide are mixed, add slipping agent and/or oxidation inhibitor.Described slipping agent and described oxidation inhibitor are all with above-described identical.The described slipping agent that contains 0-0.2 % by weight (being preferably 0.001-0.2 % by weight) in poly(lactic acid)-polyester composite that the consumption of described slipping agent and described oxidation inhibitor makes finally to prepare and the described oxidation inhibitor of 0-0.2 % by weight (being preferably 0.001-0.2 % by weight).
The present invention also provides poly(lactic acid)-polyester composite of being prepared by aforesaid method.Described poly(lactic acid)-polyester composite has good comprehensive mechanical property, particularly in the toughness aspect erosion-resisting characteristics and tensile property with improvement.And because each component in described poly(lactic acid)-polyester composite is all nontoxic with biodegradable, therefore, described poly(lactic acid)-polyester composite is eco-friendly, has good biodegradability.
The invention will be further described by the following examples.
In following examples, the melting index of polymkeric substance and matrix material, according to ISO1133-2005 " mensuration of thermoplastics melt mass flow rate and melt flow rate of volume flow " standard method, at 190 ℃, detects and obtains under the effect of 2.16kg load;
The weight-average molecular weight of polymkeric substance and molecular weight distribution coefficient are according to gel permeation chromatography (GPC), take tetrahydrofuran (THF) (THF) as solvent, at Waters-208(band Waters 2410 RI detectors, 1.5ml/min flow velocity, 30 ℃) to measure on instrument, weight-average molecular weight is calibrated with vinylbenzene standard specimen;
The second-order transition temperature (Tg) of polymkeric substance detects and obtains according to differential scanning calorimeter (DSC) assay method, concrete testing process is: on Perkin Elmer Pyris 1 determinator, each sample is heated to 250 ℃ from-100 ℃, add heat scan through both sides, heating rate is 20 ℃/min.
Embodiment 1
The present embodiment is used for illustrating described poly(lactic acid)-polyester composite of the present invention and preparation method thereof.
(1) preparation of tri-block copolyester
By terephthalic acid (1mol), 1, 4-butyleneglycol and 1, 4-succinic acid take mol ratio in 2.2:5:2.5 is added to stainless steel cauldron, temperature in reactor is increased to 230 ℃, and add wherein the tetrabutyl titanate of 0.148 gram, it is 70Pa that reactor is evacuated to absolute pressure, and react 2.7h under this pressure, after being washed and be dried, reaction product obtains light yellow solid, be aliphatic-aromatic copolyester, the weight-average molecular weight of this aliphatic-aromatic copolyester is 80, 000, molecular weight distribution coefficient is 1.20, second-order transition temperature is-12 ℃.
The above-mentioned aliphatic-aromatic copolyester of the LLA of 10 grams and 1.0 grams is added in reactor, add again the stannous octoate of 10 milligrams, mix the rear nitrogen purging 5h that uses, then under nitrogen atmosphere, reactor is positioned in the oil bath of 170 ℃, reaction 5h and cooling after, in reactor, add chloroform so that reaction product is diluted, and the mixture after dilution is precipitated in anhydrous methanol, white solid will be obtained after drying precipitate, be tri-block copolyester TP1 of the present invention, the weight-average molecular weight of this tri-block copolyester is 120, 000, molecular weight distribution coefficient is 1.6, productive rate is 90%.By AVANCE 300 nuclear magnetic resonance analyser of Bruker company of Switzerland, adopt deuterochloroform as solvent, this tri-block copolyester is carried out to nuclear magnetic resonance experiment, obtain nmr spectrum as shown in Figure 1.
(2) preparation of poly(lactic acid)-polyester composite
By 300g PLLA (purchased from Nature Works LLC company, weight-average molecular weight is 120, 000, lower same), in 30g above-mentioned steps (1), poly-(terephthalic acid butyleneglycol-succinic acid butyleneglycol) the ester P1(of the tri-block copolyester TP1 of preparation and 170g makes according to the method for Embodiment B in CN1807485A 12, GPC weight-average molecular weight is 11.1 ten thousand, molecular weight distribution coefficient is 2.05) mix, then add successively 0.5g erucicamide (purchased from Beijing Xing Beida chemical materials company limited, lower same) and 1g2, 5-dimethyl-2, two (tert-butyl peroxide) hexanes of 5-are (purchased from the same Chemical Co., Ltd. that joins, t at 177 ℃
1/2be 1 minute, lower same) mix.The material obtaining after mixing is carried out to extruding pelletization by twin screw extruder, the rotating speed control of screw rod is 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 ℃, 170 ℃, 170 ℃ and 165 ℃, thereby makes poly(lactic acid)-polyester composite A1.
Comparative example 1
Prepare poly(lactic acid)-polyester composite according to the method for embodiment 1, difference is not add the tri-block copolyester TP1 preparing in the step (1) of embodiment 1, thereby make poly(lactic acid)-polyester composite D1.
Comparative example 2
Prepare poly(lactic acid)-polyester composite according to the method for embodiment 1, difference is, do not add 2,5-dimethyl-2, two (tert-butyl peroxide) hexanes of 5-, thus make poly(lactic acid)-polyester composite D2.
Embodiment 2
The present embodiment is used for illustrating described poly(lactic acid)-polyester composite of the present invention and preparation method thereof.
The tri-block copolyester TP1 that in 300g PLLA, 60g embodiment 1 prepared by step (1) and poly-(terephthalic acid butyleneglycol-succinic acid butyleneglycol) the ester P1 of 140g are mixed, then add successively 0.5g erucicamide and 1g 2,5-dimethyl-2, two (tert-butyl peroxide) hexanes of 5-mix.The material obtaining after mixing is carried out to extruding pelletization by twin screw extruder, the rotating speed control of screw rod is 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 ℃, 170 ℃, 170 ℃ and 165 ℃, thereby makes poly(lactic acid)-polyester composite A2.
Embodiment 3
The present embodiment is used for illustrating described poly(lactic acid)-polyester composite of the present invention and preparation method thereof.
The tri-block copolyester TP1 that in 300g PLLA, 90g embodiment 1 prepared by step (1) and poly-(terephthalic acid butyleneglycol-succinic acid butyleneglycol) the ester P1 of 110g are mixed, then add successively two (t-butyl peroxy sec.-propyl) benzene of 0.5g erucicamide and 1g (purchased from upper maritime business's scape Industrial Co., Ltd., the t at 185 ℃
1/2be 1 minute) mix.The material obtaining after mixing is carried out to extruding pelletization by twin screw extruder, the rotating speed control of screw rod is 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 ℃, 170 ℃, 170 ℃ and 165 ℃, thereby makes poly(lactic acid)-polyester composite A3.
Embodiment 4
The present embodiment is used for illustrating described poly(lactic acid)-polyester composite of the present invention and preparation method thereof.
(1) preparation of tri-block copolyester
Will be to naphthalic acid (0.8mol), 1, 4-butyleneglycol and 1, 4-succinic acid take mol ratio in 1.5:5:3 is added to stainless steel cauldron, temperature in reactor is increased to 230 ℃, and add wherein the tetrabutyl titanate of 0.20 gram, it is 70Pa that reactor is evacuated to absolute pressure, and react 2.7h under this pressure, after being washed and be dried, reaction product obtains light yellow solid, be aliphatic-aromatic copolyester, the weight-average molecular weight of this aliphatic-aromatic copolyester is 100, 000, molecular weight distribution coefficient is 1.30, second-order transition temperature is-11 ℃.
The above-mentioned aliphatic-aromatic copolyester of the LLA of 30 grams and 10 grams is added in reactor, add again the stannous octoate of 80 milligrams, mix the rear nitrogen purging 5h that uses, then under nitrogen atmosphere, reactor is positioned in the oil bath of 180 ℃, reaction 5h and cooling after, in reactor, add chloroform so that reaction product is diluted, and the mixture after dilution is precipitated in anhydrous methanol, white solid will be obtained after drying precipitate, be tri-block copolyester TP2 of the present invention, the weight-average molecular weight of this tri-block copolyester is 170, 000, molecular weight distribution coefficient is 1.8, productive rate is 96%.
(2) preparation of poly(lactic acid)-polyester composite
By 150g PLLA, 150g D-poly(lactic acid) (purchased from Dutch Purac company, weight-average molecular weight is 150,000), in 30g above-mentioned steps (1), poly-(terephthalic acid butyleneglycol-hexanodioic acid butyleneglycol) the ester P2(of the tri-block copolyester TP2 of preparation and 265g makes according to the method for embodiment A in CN1807485A 7, GPC weight-average molecular weight is 10.2 ten thousand, molecular weight distribution coefficient is 2.25) mix, then add 0.3g dibenzoyl peroxide (purchased from innovation Chemical Co., Ltd. of Jinan City, the t at 133 ℃
1/2be 1 minute) mix.The material obtaining after mixing is carried out to extruding pelletization by twin screw extruder, the rotating speed control of screw rod is 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 ℃, 170 ℃, 170 ℃ and 165 ℃, thereby makes poly(lactic acid)-polyester composite A4.
Embodiment 5
The present embodiment is used for illustrating described poly(lactic acid)-polyester composite of the present invention and preparation method thereof.
(1) preparation of tri-block copolyester
By terephthalic acid (1.5mol), 1, 4-butyleneglycol and 1, 4-succinic acid take mol ratio in 3:5:1.5 is added to stainless steel cauldron, temperature in reactor is increased to 230 ℃, and add wherein the tetrabutyl titanate of 0.148 gram, it is 70Pa that reactor is evacuated to absolute pressure, and react 2.7h under this pressure, after being washed and be dried, reaction product obtains light yellow solid, be aliphatic-aromatic copolyester, the weight-average molecular weight of this aliphatic-aromatic copolyester is 80, 000, molecular weight distribution coefficient is 1.20, second-order transition temperature is-12 ℃.
The above-mentioned aliphatic-aromatic copolyester of the LLA of 10 grams and 1.0 grams is added in reactor, add again the stannous octoate of 40 milligrams, mix the rear nitrogen purging 5h that uses, then under nitrogen atmosphere, reactor is positioned in the oil bath of 190 ℃, reaction 3h and cooling after, in reactor, add chloroform so that reaction product is diluted, and the mixture after dilution is precipitated in anhydrous methanol, white solid will be obtained after drying precipitate, be tri-block copolyester TP3 of the present invention, the weight-average molecular weight of this tri-block copolyester is 150, 000, molecular weight distribution coefficient is 2.0, productive rate is 97%.
(2) preparation of poly(lactic acid)-polyester composite
The tri-block copolyester TP3 of preparation in 300g PLLA, 30g above-mentioned steps (1) and poly-(terephthalic acid butyleneglycol-hexanodioic acid butyleneglycol) the ester P3(of 170g are made according to the method for Embodiment B in CN1807485A 6, GPC weight-average molecular weight is 14.0 ten thousand, molecular weight distribution coefficient is 2.05) mix, then add successively two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic esters (purchased from Ciba-Geigy company of Switzerland) of 0.5g triglycol and 1g dicumyl peroxide (purchased from Nanjing Zhong Xu Chemical Co., Ltd., the t at 171 ℃
1/2be 1 minute) mix.The material obtaining after mixing is carried out to extruding pelletization by twin screw extruder, the rotating speed control of screw rod is 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 ℃, 170 ℃, 170 ℃ and 165 ℃, thereby makes poly(lactic acid)-polyester composite A5.
Test case
Poly-(terephthalic acid butyleneglycol-succinic acid butyleneglycol) the ester P1 using in tri-block copolyester TP1 prepared by the PLLA using in poly(lactic acid)-polyester composite prepared by above-described embodiment and comparative example and embodiment 1, the step (1) of embodiment 1 and embodiment 1 makes respectively melting compressing tablet, and the press sheet compression of making is carried out to Mechanics Performance Testing and biodegradability test.Particularly, the tensile mechanical properties that detects these press sheet compressions according to GB/T 1040.2-2006 method is as stretching yield stress, tensile break stress, tension fracture elongation rate and simply supported beam notched Izod impact strength; Detect the biodegradability of these press sheet compressions according to the method for GB/T20197-2006, and the mass loss of press sheet compression before with respect to test accounts for the weight percent of press sheet compression before test and recently represents biological degradation rate with the press sheet compression after test.
Detected result is as shown in table 1 below.
Table 1
NB refers to that punching constantly.
The data of recording according to above-mentioned table 1, compare and can find out by the press sheet compression that poly(lactic acid)-polyester composite of being prepared by embodiment 1 is made and the press sheet compression of being made by the poly(lactic acid)-polyester composite of comparative example 1 and 2 preparations, the erosion-resisting characteristics of the press sheet compression that poly(lactic acid)-polyester composite of being prepared by embodiment 1 is made and tensile property are all better, show good comprehensive mechanical property; Compare and can find out by the press sheet compression that poly(lactic acid)-polyester composite of being prepared by embodiment 1 is made and the press sheet compression of being made by PLLA and P1, the toughness (as tensile property) that poly(lactic acid)-polyester composite according to the present invention has clear improvement with respect to poly(lactic acid) tool, the rigidity (as resistance to impact shock) that the aliphatics aromatic copolyester tool random with respect to linearity has clear improvement.As can be seen here, poly(lactic acid)-polyester composite according to the present invention has preferably comprehensive mechanical property.
And, being it can also be seen that by the data of table 1, poly(lactic acid)-polyester composite according to the present invention has preferably biodegradability.
Claims (10)
1. poly(lactic acid)-polyester composite, this matrix material contains poly(lactic acid), linear random aliphatics aromatic copolyester, tri-block copolyester and organo-peroxide, wherein, the structural formula of described tri-block copolyester as shown in Equation 1:
Formula 1
Wherein, the integer that p is 5-200, the integer that q is 5-200, M comprises the structural unit as shown in following formula 2 and formula 3,
Formula 2
Formula 3
Wherein, Ar is the group with phenyl ring, naphthalene nucleus or anthracene nucleus; M is the integer of 1-20, the integer that n is 1-16, the integer that t is 1-20;
The mol ratio of the structural unit shown in formula 2 and formula 3 is 1:0.1-10, and the weight-average molecular weight of M section is 6000-600,000, and the weight-average molecular weight of described tri-block copolyester is 10,000-1,000,000;
The random aliphatics aromatic copolyester of described linearity comprises as shown in the formula the structural unit shown in 4:
Wherein, a is the integer of 2-10, b is the integer of 0-8, the integer that c is 2-10, and a, b and c are identical or different, d is the integer of 1-10, e is the integer of 1-10, and the weight-average molecular weight of the random aliphatics aromatic copolyester of described linearity is 100,000-600,000, molecular weight distribution coefficient is 1.2-3.
2. matrix material according to claim 1, wherein, take the gross weight of described poly(lactic acid)-polyester composite as benchmark, the content of described poly(lactic acid) is 10-90 % by weight, is preferably 50-70 % by weight; The content of the random aliphatics aromatic copolyester of described linearity is 5-70 % by weight, is preferably 20-45 % by weight; The content of described tri-block copolyester is 1-20 % by weight, is preferably 5-18 % by weight; The content of described organo-peroxide is 0.01-1 % by weight, is preferably 0.05-0.2 % by weight.
3. matrix material according to claim 1 and 2, wherein, in formula 1, the integer that p is 10-100, the integer that q is 10-100; In formula 2, the integer that m is 2-10, the integer that n is 2-8; In formula 3, the integer that t is 2-10; The mol ratio of the structural unit shown in formula 2 and formula 3 is 1:0.5-2, and the weight-average molecular weight of M section is 60,000-120,000, and the weight-average molecular weight of described tri-block copolyester is 80,000-600,000.
4. matrix material according to claim 1 and 2, wherein, Ar is following aryl:
Wherein, R
1, R
2, R
3, R
4, R
5and R
6be alkyl, F, the Cl ,-NO of hydrogen, C1-C4 independently of one another
2,-CN or-OR
7, wherein, R
7for the alkyl of C1-C4.
5. matrix material according to claim 1 and 2, wherein, the weight-average molecular weight of described poly(lactic acid) is 80,000-200,000.
6. matrix material according to claim 1 and 2, wherein, in formula 4, the integer that a is 2-4, the integer that b is 2-4, the integer that c is 2-4, the integer that d is 1-3, the integer that e is 1-2.
7. matrix material according to claim 1 and 2, wherein, the weight-average molecular weight of the random aliphatics aromatic copolyester of described linearity is 100,000-300,000, molecular weight distribution coefficient is 1.5-2.5.
8. matrix material according to claim 1 and 2; wherein; described organo-peroxide is at least one in dialkyl, peroxidation diacyl and peroxyester; be preferably dicumyl peroxide, 2; 5-dimethyl-2, at least one in two (tert-butyl peroxide) hexanes of 5-, two (t-butyl peroxy sec.-propyl) benzene, dibenzoyl peroxide, lauroyl peroxide and tert-butyl hydroperoxide isobutyrate.
9. the preparation method of the poly(lactic acid)-polyester composite described in any one in claim 1-8, the method comprises: poly(lactic acid), aliphatics aromatic copolyester, tri-block copolyester and organo-peroxide are mixed, and the mixture obtaining is carried out to extruding pelletization.
10. poly(lactic acid)-polyester composite of being prepared by method claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210420781.0A CN103788599B (en) | 2012-10-29 | 2012-10-29 | A kind of poly(lactic acid)-polyester composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210420781.0A CN103788599B (en) | 2012-10-29 | 2012-10-29 | A kind of poly(lactic acid)-polyester composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103788599A true CN103788599A (en) | 2014-05-14 |
| CN103788599B CN103788599B (en) | 2015-11-25 |
Family
ID=50664681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210420781.0A Active CN103788599B (en) | 2012-10-29 | 2012-10-29 | A kind of poly(lactic acid)-polyester composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103788599B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018072748A1 (en) * | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition and preparation method therefor |
| CN116003971A (en) * | 2022-10-19 | 2023-04-25 | 张余 | High-strength high-toughness biodegradable plastic and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020198332A1 (en) * | 2000-07-17 | 2002-12-26 | Tomoyuki Kasemura | Lactic-acid base resin composition and molded articles made therefor |
| US20080042312A1 (en) * | 2006-06-27 | 2008-02-21 | Far Eastern Textile Ltd. | Deep-dyeable modified polylactic acid fiber |
| CN101245178A (en) * | 2008-03-06 | 2008-08-20 | 同济大学 | Method for manufacturing biologically degradable polyester composite material with capacity increasing function |
| CN101717493A (en) * | 2009-11-09 | 2010-06-02 | 浙江杭州鑫富药业股份有限公司 | Aliphatic-aromatic copolyester, preparation method and application thereof |
| CN102295825A (en) * | 2011-07-08 | 2011-12-28 | 金发科技股份有限公司 | Biodegradable composition and preparation method thereof |
| CN102660008A (en) * | 2012-05-14 | 2012-09-12 | 浙江杭州鑫富药业股份有限公司 | Aliphatic-aromatic copolyester and PLA (Poly Lactic Acid) block copolymer and production method and application thereof and composition containing block copolymer |
-
2012
- 2012-10-29 CN CN201210420781.0A patent/CN103788599B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020198332A1 (en) * | 2000-07-17 | 2002-12-26 | Tomoyuki Kasemura | Lactic-acid base resin composition and molded articles made therefor |
| US20080042312A1 (en) * | 2006-06-27 | 2008-02-21 | Far Eastern Textile Ltd. | Deep-dyeable modified polylactic acid fiber |
| CN101245178A (en) * | 2008-03-06 | 2008-08-20 | 同济大学 | Method for manufacturing biologically degradable polyester composite material with capacity increasing function |
| CN101717493A (en) * | 2009-11-09 | 2010-06-02 | 浙江杭州鑫富药业股份有限公司 | Aliphatic-aromatic copolyester, preparation method and application thereof |
| CN102295825A (en) * | 2011-07-08 | 2011-12-28 | 金发科技股份有限公司 | Biodegradable composition and preparation method thereof |
| CN102660008A (en) * | 2012-05-14 | 2012-09-12 | 浙江杭州鑫富药业股份有限公司 | Aliphatic-aromatic copolyester and PLA (Poly Lactic Acid) block copolymer and production method and application thereof and composition containing block copolymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018072748A1 (en) * | 2016-10-21 | 2018-04-26 | 中国石油化工股份有限公司 | Polyester composition and preparation method therefor |
| US10934391B2 (en) | 2016-10-21 | 2021-03-02 | China Petroleum & Chemical Corporation | Polyester composition and preparation method therefor |
| CN116003971A (en) * | 2022-10-19 | 2023-04-25 | 张余 | High-strength high-toughness biodegradable plastic and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103788599B (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103788600B (en) | A kind of poly(lactic acid)-polyester composite and preparation method thereof | |
| CN102838734B (en) | Polylactic acid block polymer and preparation method thereof | |
| CN102838856B (en) | Biodegradable compound and preparation method thereof and disposablearticle | |
| US20230323114A1 (en) | Aliphatic-polyester-based resin composition and utilization thereof | |
| CN105623211B (en) | A kind of poly (lactic acid) composition and preparation method thereof | |
| CN104592503B (en) | A kind of polylactic acid tri-block copolyesters and preparation method thereof | |
| CN102060986A (en) | Aromatic-aliphatic block copolyester and preparation method thereof | |
| JP2021102669A (en) | Aliphatic polyester resin composition and its usage | |
| CN109776809B (en) | Easily-crosslinked biodegradable resin and preparation method thereof | |
| CN113968961A (en) | Poly (terephthalic acid) -co-butylene succinate-polylactic acid copolymer and preparation method thereof | |
| CN102443145B (en) | Tri-block copolyester and preparation method thereof | |
| CN102838855B (en) | Biodegradable composite, disposable product and preparation method thereof | |
| CN103788599B (en) | A kind of poly(lactic acid)-polyester composite and preparation method thereof | |
| CN106939077A (en) | A kind of Biodegradable three-element copolymerized ester PBAST synthetic process | |
| CN102838854B (en) | Biodegradable composite, disposable product and preparation method thereof | |
| CN102942687A (en) | Flame-retardant aliphatic-aromatic copolyester and preparation method thereof | |
| CN105531320A (en) | Resin composition containing polyalkylene carbonate | |
| CN102924676A (en) | Transparent copolyester and its preparation method | |
| JP4975296B2 (en) | Polylactic acid copolymer resin and method for producing the same | |
| Dong et al. | High performance and water‐degradable poly (neopentyl terephthalate‐co‐neopentyl succinate) copolymers: Synthesis, properties, and hydrolysis in different aquatic bodies | |
| CN104592521A (en) | Binary block aliphatic copolyester and preparation method thereof | |
| KR102069509B1 (en) | Biodegradable poly(butylene tetramethyleneglutarate-co-butylene terephthalate) aliphatic and aromatic polyester resin and the manufacturing method thereof | |
| JPH083296A (en) | Aliphatic polyester copolymer and its production | |
| JP2008115289A (en) | Method for producing polylactic acid copolymer resin | |
| US20240336730A1 (en) | Semi-aromatic polyether ester, preparation method therefor and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |