CN103788599B - A kind of poly(lactic acid)-polyester composite and preparation method thereof - Google Patents
A kind of poly(lactic acid)-polyester composite and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of poly(lactic acid)-polyester composite, this matrix material contains poly(lactic acid), linearly random aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide.The preparation method that the invention still further relates to described poly(lactic acid)-polyester composite and the poly(lactic acid)-polyester composite prepared by the method, the method comprises: poly(lactic acid), aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide are mixed, and the mixture obtained is carried out extruding pelletization.Poly(lactic acid)-polyester composite according to the present invention has preferably comprehensive mechanical property and biodegradability.
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 the poly(lactic acid)-polyester composite prepared by the method.
Background technology
Poly(lactic acid) is as the Biodegradable material coming from bio-based, because it has broken away from unique dependency of petroleum resources, and product after a procedure can be degradable under the effect of microorganism, final product is carbonic acid gas and water, return the natural track of Life Cycles, its significant low-carbon (LC) is load, biocompatibility, biodegradation character and good mechanical property and use properties, and other any material all cannot be equal to it at present.But the defect such as the fragility that poly-lactic acid material self shows because of higher second-order transition temperature (about 50-60 DEG C) and the poor heat resistance that causes because self softening temperature is low significantly limit the application of poly(lactic acid).Therefore, domestic and international investigators are devoted to have carried out large quantifier elimination to the toughness reinforcing of poly(lactic acid) and thermotolerance one after another.
Carry out toughening modifying to poly(lactic acid) mainly to be undertaken by copolymerization and blended mode.Modification by copolymerization complex process, the production cycle is long, and cost is high, more difficult enforcement, is difficult to industrialization continuous seepage.Therefore, blended mode is adopted to carry out to poly(lactic acid) toughening modifying to become toughening modifying preferred version owing to easily implementing on existing apparatus.For toughening modifying, best toughner is exactly the elastomer material of rubber-like, as the MBS used in CN101875763A, the olefin(e) compound of the ethylene copolymer used in CN101495568A, US20100112357 and US20060263394 or band epoxy-functional is as impact modifier and plasticized modifier etc., but this kind of material self is non-degradable material, after mixing with poly(lactic acid), the biodegradation character of material can be affected, lose the original environmental protection superiority differing from other material of poly(lactic acid) on the contrary.Therefore, Biodegradable material is used to be the optimal selection to poly(lactic acid) toughening modifying as polylactic acid toughening modifier.
Mention in CN1392891A and US20020198332 and poly(lactic acid) is mixed with aliphatic polyester, add the segmented copolymer of the two as expanding material simultaneously, spinning and the tensile property of poly(lactic acid) can be improved.Refer to the tertiary mixture that poly(lactic acid) and PHA and aliphatic polyester form in US20020151618 and US20040092672, soft film material can be prepared.All mention the tertiary mixture using poly(lactic acid) and other degradable polyester or copolyesters to form in US20070203291, CN1531573A and CN1489616A and there is extraordinary tear resistance etc.Mention preparation poly(lactic acid) in CN101024696A and aliphatic poly esterdiol carries out chain extending reaction under the existence of chainextender vulcabond, prepare block polymer, good toughness, tensile strength is large and tension set is high poly-lactic acid material can be obtained.Toughening modifying effect toughening effect in anti-impact and tensile property of above-mentioned blend is still very limited, be that its tension set of material of external phase is difficult to meet or exceed 300% with poly(lactic acid), and the notched Izod impact hit intensity of material does not have clear improvement.In addition, carry out modification with vulcabond as chainextender and can bring certain toxicity to material.
Summary of the invention
The toughening effect in erosion-resisting characteristics and tensile property that the object of the invention is to overcome the existence of existing poly(lactic acid) toughening modifying method is limited, or the defect that modified meeting brings toxicity or biodegradability obviously to reduce relative to poly(lactic acid), provides a kind of poly(lactic acid)-polyester composite and preparation method thereof.
The invention provides a kind of poly(lactic acid)-polyester composite, this matrix material contains poly(lactic acid), linearly random aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide, wherein, the structural formula of described tri-block copolyester as shown in Equation 1:
Formula 1
Wherein, p is the integer of 5-200, and q is the integer of 5-200, and 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, and n is the integer of 1-16, and t is the integer of 1-20;
The mol ratio of the structural unit shown in formula 2 and formula 3 is the weight-average molecular weight of 1:0.1-10, M section is 6000-600,000, and the weight-average molecular weight of described tri-block copolyester is 10,000-1,000,000;
Described linearly random aliphatic aromatic copolyesters 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, and c is the integer of 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 described linearly random aliphatic aromatic copolyesters is 100,000-600,000, molecular weight distribution index is 1.2-3.
Present invention also offers the preparation method of described poly(lactic acid)-polyester composite, the method comprises: poly(lactic acid), linearly random aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide are mixed, and the mixture obtained is carried out extruding pelletization.
Present invention also offers the poly(lactic acid)-polyester composite prepared by aforesaid method.
In described poly(lactic acid)-polyester composite provided by the invention, organo-peroxide and described tri-block copolyester can not only strengthen the consistency of the mixed system of poly(lactic acid) and linearly random aliphatic aromatic copolyesters, but also the effect of chain extension increase-volume can be played, thus make described poly(lactic acid)-polyester composite comprehensive mechanical property better, particularly there is the toughness of improvement in erosion-resisting characteristics and tensile property.
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 in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 represents the nmr spectrum of the tri-block copolyester used in embodiment 1.
Embodiment
The invention provides a kind of poly(lactic acid)-polyester composite, this matrix material contains poly(lactic acid), linearly random aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide, wherein, the structural formula of described tri-block copolyester as shown in Equation 1:
Formula 1
Wherein, p is the integer of 5-200, and q is the integer of 5-200, and 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, and n is the integer of 1-16, and t is the integer of 1-20;
The mol ratio of the structural unit shown in formula 2 and formula 3 is the weight-average molecular weight of 1:0.1-10, M section is 6000-600,000, and the weight-average molecular weight of described tri-block copolyester is 10,000-1,000,000;
Described linearly random aliphatic aromatic copolyesters 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, and c is the integer of 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 described linearly random aliphatic aromatic copolyesters is 100,000-600,000, molecular weight distribution index is 1.2-3.
In the present invention, the weight-average molecular weight of polymkeric substance and molecular weight distribution index record according to gel permeation chromatography (GPC).
In the present invention, in order to obtain the poly(lactic acid)-polyester composite of toughness and the good biodegradability with improvement, mainly by adding in the compound system to poly(lactic acid) and linearly random aliphatic aromatic copolyesters, the described tri-block copolyester that can play chain extension increase-volume and described organo-peroxide realize.As long as owing to adding described tri-block copolyester and described organo-peroxide, their chain extension compatibilization will be clearly, therefore, in described poly(lactic acid)-polyester composite, there is no particular limitation for described poly(lactic acid), described linearly random aliphatic aromatic copolyesters, described tri-block copolyester and described organo-peroxide content.In the preferred case, there is to make described poly(lactic acid)-polyester composite the toughness and comprehensive mechanical property improved further, with the gross weight of described poly(lactic acid)-polyester composite for benchmark, the content of described poly(lactic acid) is 10-90 % by weight, the content of described linearly random aliphatic aromatic copolyesters 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, with the gross weight of described poly(lactic acid)-polyester composite for benchmark, the content of described poly(lactic acid) is 50-70 % by weight; The content of described linearly random aliphatic aromatic copolyesters 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 hydrogen, the alkyl of C1-C4, F, Cl ,-NO 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, when M is alternating copolymerization segment, M can for 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, are preferably the integer of 10-100.
When M is block copolymerization segment, M can for 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, are 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.
When 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, and in the structural unit shown in any two formulas 6 of M, u and/or v is different, 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 the method for routine.In the preferred case, described tri-block copolyester can method preparation disclosed in CN102443145A.Particularly, the preparation method of described tri-block copolyester can comprise: under the existence of organo-tin compound, under esterification condition, under an inert atmosphere, linear type aliphatic aromatic copolyester is contacted with rac-Lactide, described linear type aliphatic aromatic copolyester comprises the structural unit as shown in following formula 2 and formula 3
Formula 2
Formula 3
Wherein, m is the integer of 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 linear type aliphatic 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 hydrogen, the alkyl of C1-C4, F, Cl ,-NO 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 linear type aliphatic aromatic copolyester can be at least one in alternating copolymer, segmented copolymer and random copolymers, is preferably alternating copolymer and/or segmented copolymer.Described linear type aliphatic aromatic copolyester can be commercially available (such as can purchased from BASF Aktiengesellschaft), also can obtain according to the method for routine, the preparation method of this linear type aliphatic 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 DEG C polycondensation occur, described polycondensation catalyst such as can 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, relative to the rac-Lactide of 100 weight parts, the consumption of described linear type aliphatic 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 DEG C, is preferably 150-190 DEG C, is more preferably 170-190 DEG C; 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 at ambient pressure, but, speed of response can also be improved further under an increased pressure.
In the preparation method of above-mentioned tri-block copolyester, described inert atmosphere refers to the environment formed by the gas do not reacted with described linear type aliphatic aromatic series and rac-Lactide, and this gas can be the rare gas element of nitrogen and routine.
Described organo-tin compound can be the organo-tin compound being used as the catalyzer of esterification of various routine, 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 isolating tri-block copolyester of the present invention the product obtained after esterification can comprise: the product obtained after making esterification mixes with chloroform, and the mixture obtained is precipitated, then by drying precipitate in methyl alcohol and/or ethanol.
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 routine, such as, can be PLLA (PLLA) and/or D-poly(lactic acid) (PDLA).In the preferred case, described poly(lactic acid) contains the PDLA of PLLA and 0-50 % by weight of 50-100 % by weight.
As described linearly random aliphatic aromatic copolyesters, 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 described linearly random aliphatic aromatic copolyesters, its weight-average molecular weight is preferably 100,000-300, and 000, molecular weight distribution index is preferably 1.5-2.5.
The fusing point of described linearly random aliphatic aromatic copolyesters can be 20-185 DEG C.
The second-order transition temperature (Tg) of described linearly random aliphatic aromatic copolyesters can be-55 DEG C to-7 DEG C.In the present invention, the second-order transition temperature of polymkeric substance detects according to differential scanning calorimeter (DSC) assay method and obtains.
Described linearly random aliphatic aromatic copolyesters can prepare according to the method for routine.In the preferred case, described linearly random aliphatic aromatic copolyesters can method preparation disclosed in CN1807485A.Particularly, the preparation method of described linearly random aliphatic aromatic copolyesters can comprise the following steps:
(1) will add in reactor with lower unit and nonessential catalyst component Cat1 and carry out transesterification reaction and/or esterification: the ester of (a) aromatic acid, aromatic acid, aromatic dicarboxylic anhydride or their arbitrary combination; (b) aliphatic dihydroxy alcohol, cycloaliphatic diols or their arbitrary combination; And (c) aliphatic dibasic acid, cycloaliphatic diacid, their ester, their acid anhydrides or their arbitrary combination, wherein, (a) can be 5:95 to 75:25 with the mol ratio of (c);
(2) under vacuum, the reaction product that step (1) obtains is carried out pre-polymerization; And
(3) add catalyst component Cat2 in the prepolymer product obtained to step (2), carry out vacuum polycondensation, thus obtained linearly random aliphatic aromatic copolyesters;
Wherein, described catalyst component Cat1 is selected from the compound of metal titanium, the compound of antimony, the compound of zinc and their arbitrary combination;
Described catalyst component Cat2 is the compound and the arbitrary combination thereof that are selected from metal Ln, and wherein said metal Ln is at least one in lanthanon, scandium and yttrium.
In step (1), first aromatic monomer (a) and glycol monomer (b) can be reacted, and then add aliphatic monomer (c); Also first aliphatic monomer (c) and glycol monomer (b) can be reacted, and then add aromatic monomer (a).Preferably, in step (1), first described catalyst component Cat1, monomer (a) and monomer (b) are added reactor to react; And then add monomer (c) and 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 DEG C, carry out the first step esterification or transesterification reaction, when small molecules cut to be received reaches more than 90 % by weight of theoretical amount, add monomer (c), preferably at 160-250 DEG C, carry out second step esterification or transesterification reaction, when small molecules cut to be received reaches more than 90 % by weight of theoretical amount, carry out follow-up pre-collecting process.
Above-mentioned two step esterifications or transesterification reaction can be carried out under normal pressure, vacuum and pressurized state, preferably carry out at ambient pressure.
The pre-collecting process of step (2) preferably 190-250 DEG C, vacuum tightness is that 200-600Pa(is preferably 200-300Pa) 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 absolute pressure represents.
In step (3), the temperature of polycondensation is preferably 200-300 DEG C, is more preferably 220-280 DEG C.Described polycondensation is preferably carry out under the condition of below 300Pa (being more preferably below 200Pa) in vacuum tightness.The time of described polycondensation can be 3-8 hour.
In the preparation method of above-mentioned linearly random aliphatic aromatic copolyesters, step (1) to (3) can be carried out in same reactor.
Monomer (a) is preferably 5:95 to 65:35 with the mol ratio of monomer (c), is more preferably 35:65 to 60:40.Monomer (a) is preferably 1:1-3 with the mole number sum of monomer (c) and the mol ratio of monomer (b), is more preferably 1:1-2, 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 phenyl diprotic acid, to the ester of phenyl diprotic acid with at least one in phenyl dibasic acid anhydride, is more preferably terephthalic acid and/or dimethyl terephthalate (DMT).
Monomer (b) is preferably the aliphatic dihydroxy alcohol of C2-C6 and/or the cycloaliphatic diols 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 cycloaliphatic diacid 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)
fwith M (-OOCR
2)
gin one or more, wherein, M is titanium, antimony or zinc, f and g is the valence state of M independently of one another, R
1for C
1-C
10alkyl, R
2for C
1-C
30alkyl; Be more preferably titan-alkoxide (Ti (OR
1)
f), at least one in the oxide compound of zinc acetate, zinc, the oxide compound of antimony and titanyl compound; At least one more preferably 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, is more preferably 2:3 to 3:2.
In described poly(lactic acid)-polyester composite of the present invention, described organo-peroxide can for playing the organo-peroxide of 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, preferred further, described organo-peroxide is dicumyl peroxide, 2, at least one in 5-dimethyl-2,5-two (tert-butyl peroxide) hexane, two (tert-butylperoxyiso-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, such as, can also contain slipping agent and/or oxidation inhibitor.Described slipping agent can be conventionally used as the material of slipping agent for this area, such as, can be take lipid acid as the aminocompound of substrate, as erucicamide, amine hydroxybenzene, stearic amide fourth.Described oxidation inhibitor can be conventionally used as the material of oxidation inhibitor for this area, it can be such as hindered phenol type antioxidant, β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester as two in triglycol (being called for short oxidation inhibitor 245) and/or 3,5-di-t-butyl-4 hydroxy-phenylpropionic acid octadecanol ester (abbreviation antioxidant 1076).In described poly(lactic acid)-polyester composite, with the gross weight of described poly(lactic acid)-polyester composite for 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.
Present invention also offers a kind of method preparing poly(lactic acid)-polyester composite, the method comprises: poly(lactic acid), linearly random aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide are mixed, and the mixture obtained is carried out extruding pelletization.
Described poly(lactic acid), described linearly random aliphatic aromatic copolyesters, described tri-block copolyester and described organo-peroxide all with describe above identical.
Described poly(lactic acid), described linearly random aliphatic aromatic copolyesters, described tri-block copolyester and the equal consumption of described organo-peroxide preferably make the described poly(lactic acid) containing 10-90 % by weight (being preferably 50-70 % by weight) in the poly(lactic acid)-polyester composite of final preparation, the described linearly random aliphatic aromatic copolyesters of 5-70 % by weight (being preferably 20-45 % by weight), the described tri-block copolyester of 1-20 % by weight (being preferably 5-18 % by weight) and the described organo-peroxide of 0.01-1 % by weight (being preferably 0.05-0.2 % by weight).
Poly(lactic acid), linearly random aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide are being carried out in the process 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.
When described organo-peroxide mixes with other components with the form of organic solution, described method preferably also comprises carries out drying by the mixture obtained in described mixing process.Described drying such as can carry out 1-2 days in loft drier at 50-60 DEG C.
Described extruding pelletization process can extruding pelletization method conveniently be implemented.Under preferable case, described extruding pelletization process is carried out at 80-180 DEG C 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 DEG C, 165-170 DEG C, 165-170 DEG C and 160-165 DEG C from opening for feed to extrusion.
In the present invention, the described method preparing poly(lactic acid)-polyester composite can also comprise: poly(lactic acid), linearly random aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide are being carried out, in the process mixed, adding slipping agent and/or oxidation inhibitor.Described slipping agent and described oxidation inhibitor are all identical with above-described.The consumption of described slipping agent and described oxidation inhibitor makes to contain the described slipping agent of 0-0.2 % by weight (being preferably 0.001-0.2 % by weight) and the described oxidation inhibitor of 0-0.2 % by weight (being preferably 0.001-0.2 % by weight) in the poly(lactic acid)-polyester composite of final preparation.
Present invention also offers the poly(lactic acid)-polyester composite prepared by aforesaid method.Described poly(lactic acid)-polyester composite has good comprehensive mechanical property, in erosion-resisting characteristics and tensile property, particularly have the toughness of 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 the examples below, the melting index of polymkeric substance and matrix material, according to ISO1133-2005 " mensuration of thermoplastics melt mass flow rate and melt flow volume flow rate " standard method, at 190 DEG C, detects under the effect of 2.16kg load and obtains;
The weight-average molecular weight of polymkeric substance and molecular weight distribution index are according to gel permeation chromatography (GPC), with tetrahydrofuran (THF) (THF) for solvent, be with Waters2410RI detector at Waters-208(, 1.5ml/min flow velocity, 30 DEG C) instrument to be measured, weight-average molecular weight is calibrated with vinylbenzene standard specimen;
The second-order transition temperature (Tg) of polymkeric substance detects according to differential scanning calorimeter (DSC) assay method and obtains, concrete testing process is: on PerkinElmerPyris1 determinator, each sample is heated to 250 DEG C from-100 DEG C, through both sides heat scan, heating rate is 20 DEG C/min.
Embodiment 1
The present embodiment is for illustration of 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 is that 2.2:5:2.5 is added in stainless steel cauldron with mol ratio, temperature in reactor is increased to 230 DEG C, and add the tetrabutyl titanate of 0.148 gram wherein, reactor being evacuated to absolute pressure is 70Pa, and react 2.7h at this pressure, light yellow solid is obtained by after reaction product washing also drying, be aliphatic-aromatic copolyester, the weight-average molecular weight of this aliphatic-aromatic copolyester is 80, 000, molecular weight distribution index is 1.20, second-order transition temperature is-12 DEG C.
The above-mentioned aliphatic-aromatic copolyester of the LLA of 10 grams and 1.0 gram is added in reactor, add the stannous octoate of 10 milligrams again, mix rear nitrogen purging 5h, then in a nitrogen atmosphere reactor is positioned in the oil bath of 170 DEG C, after reaction 5h also cools, chloroform is added reaction product to be diluted in reactor, and the mixture after dilution is precipitated in anhydrous methanol, white solid is obtained by 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 index is 1.6, productive rate is 90%.By the AVANCE300 nuclear magnetic resonance analyser of Bruker company of Switzerland, adopt deuterochloroform as solvent, nuclear magnetic resonance experiment is carried out to this tri-block copolyester, obtains nmr spectrum as shown in Figure 1.
(2) preparation of poly(lactic acid)-polyester composite
By 300gL-poly(lactic acid) (purchased from NatureWorksLLC company, weight-average molecular weight is 120, 000, lower same), poly-(terephthalic acid butyleneglycol-succinic acid butyleneglycol) ester P1(of tri-block copolyester TP1 and 170g of preparation in 30g above-mentioned steps (1) obtains according to the method for Embodiment B in CN1807485A 12, GPC weight-average molecular weight is 11.1 ten thousand, molecular weight distribution index is 2.05) mixing, then 0.5g erucicamide is added successively (purchased from Beijing Xing Beida chemical materials company limited, lower same) and 1g2, 5-dimethyl-2, two (tert-butyl peroxide) hexane of 5-(joins Chemical Co., Ltd. purchased from same, t at 177 DEG C
1/2be 1 minute, lower same) mix.The material obtained after mixing is carried out extruding pelletization by twin screw extruder, the rotating speed of screw rod controls to be 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 DEG C, 170 DEG C, 170 DEG C and 165 DEG C, thus obtained poly(lactic acid)-polyester composite A1.
Comparative example 1
Prepare poly(lactic acid)-polyester composite according to the method for embodiment 1, difference is, does not add the tri-block copolyester TP1 of preparation in the step (1) of embodiment 1, thus obtained poly(lactic acid)-polyester composite D1.
Comparative example 2
Prepare poly(lactic acid)-polyester composite according to the method for embodiment 1, difference is, does not add two (tert-butyl peroxide) hexane of 2,5-dimethyl-2,5-, thus obtained poly(lactic acid)-polyester composite D2.
Embodiment 2
The present embodiment is for illustration of described poly(lactic acid)-polyester composite of the present invention and preparation method thereof.
Poly-(terephthalic acid butyleneglycol-succinic acid butyleneglycol) the ester P1 of tri-block copolyester TP1 and 140g step (1) in 300gL-poly(lactic acid), 60g embodiment 1 prepared mixes, then 0.5g erucicamide and 1g2 is added successively, two (tert-butyl peroxide) hexane of 5-dimethyl-2,5-mixes.The material obtained after mixing is carried out extruding pelletization by twin screw extruder, the rotating speed of screw rod controls to be 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 DEG C, 170 DEG C, 170 DEG C and 165 DEG C, thus obtained poly(lactic acid)-polyester composite A2.
Embodiment 3
The present embodiment is for illustration of described poly(lactic acid)-polyester composite of the present invention and preparation method thereof.
Poly-(terephthalic acid butyleneglycol-succinic acid butyleneglycol) the ester P1 of tri-block copolyester TP1 and 110g step (1) in 300gL-poly(lactic acid), 90g embodiment 1 prepared mixes, then add successively two (tert-butylperoxyiso-propyl) benzene of 0.5g erucicamide and 1g (purchased from upper maritime business's scape Industrial Co., Ltd., the t at 185 DEG C
1/2be 1 minute) mix.The material obtained after mixing is carried out extruding pelletization by twin screw extruder, the rotating speed of screw rod controls to be 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 DEG C, 170 DEG C, 170 DEG C and 165 DEG C, thus obtained poly(lactic acid)-polyester composite A3.
Embodiment 4
The present embodiment is for illustration of described poly(lactic acid)-polyester composite of the present invention and preparation method thereof.
(1) preparation of tri-block copolyester
Will to naphthalic acid (0.8mol), 1, 4-butyleneglycol and 1, 4-succinic acid is that 1.5:5:3 is added in stainless steel cauldron with mol ratio, temperature in reactor is increased to 230 DEG C, and add the tetrabutyl titanate of 0.20 gram wherein, reactor being evacuated to absolute pressure is 70Pa, and react 2.7h at this pressure, light yellow solid is obtained by after reaction product washing also drying, be aliphatic-aromatic copolyester, the weight-average molecular weight of this aliphatic-aromatic copolyester is 100, 000, molecular weight distribution index is 1.30, second-order transition temperature is-11 DEG C.
The above-mentioned aliphatic-aromatic copolyester of the LLA of 30 grams and 10 gram is added in reactor, add the stannous octoate of 80 milligrams again, mix rear nitrogen purging 5h, then in a nitrogen atmosphere reactor is positioned in the oil bath of 180 DEG C, after reaction 5h also cools, chloroform is added reaction product to be diluted in reactor, and the mixture after dilution is precipitated in anhydrous methanol, white solid is obtained by 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 index is 1.8, productive rate is 96%.
(2) preparation of poly(lactic acid)-polyester composite
By 150gL-poly(lactic acid), 150gD-poly(lactic acid) (purchased from Dutch Purac company, weight-average molecular weight is 150,000), poly-(terephthalic acid butyleneglycol-hexanodioic acid butyleneglycol) the ester P2(of tri-block copolyester TP2 and 265g of preparation in 30g above-mentioned steps (1) obtains according to the method for embodiment A in CN1807485A 7, GPC weight-average molecular weight is 10.2 ten thousand, molecular weight distribution index is 2.25) mixing, then add 0.3g dibenzoyl peroxide and (innovate Chemical Co., Ltd. purchased from Jinan City, the t at 133 DEG C
1/2be 1 minute) mix.The material obtained after mixing is carried out extruding pelletization by twin screw extruder, the rotating speed of screw rod controls to be 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 DEG C, 170 DEG C, 170 DEG C and 165 DEG C, thus obtained poly(lactic acid)-polyester composite A4.
Embodiment 5
The present embodiment is for illustration of 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 is that 3:5:1.5 is added in stainless steel cauldron with mol ratio, temperature in reactor is increased to 230 DEG C, and add the tetrabutyl titanate of 0.148 gram wherein, reactor being evacuated to absolute pressure is 70Pa, and react 2.7h at this pressure, light yellow solid is obtained by after reaction product washing also drying, be aliphatic-aromatic copolyester, the weight-average molecular weight of this aliphatic-aromatic copolyester is 80, 000, molecular weight distribution index is 1.20, second-order transition temperature is-12 DEG C.
The above-mentioned aliphatic-aromatic copolyester of the LLA of 10 grams and 1.0 gram is added in reactor, add the stannous octoate of 40 milligrams again, mix rear nitrogen purging 5h, then in a nitrogen atmosphere reactor is positioned in the oil bath of 190 DEG C, after reaction 3h also cools, chloroform is added reaction product to be diluted in reactor, and the mixture after dilution is precipitated in anhydrous methanol, white solid is obtained by 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 index is 2.0, productive rate is 97%.
(2) preparation of poly(lactic acid)-polyester composite
Poly-for tri-block copolyester TP3 and 170g of preparation in 300gL-poly(lactic acid), 30g above-mentioned steps (1) (terephthalic acid butyleneglycol-hexanodioic acid butyleneglycol) ester P3(is obtained according to the method for Embodiment B in CN1807485A 6, GPC weight-average molecular weight is 14.0 ten thousand, molecular weight distribution index is 2.05) mixing, then add successively two β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (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 DEG C
1/2be 1 minute) mix.The material obtained after mixing is carried out extruding pelletization by twin screw extruder, the rotating speed of screw rod controls to be 30 revs/min, in twin screw extruder, from opening for feed to extrusion, the temperature of each section is followed successively by 100 DEG C, 170 DEG C, 170 DEG C and 165 DEG C, thus obtained poly(lactic acid)-polyester composite A5.
Test case
Poly-(terephthalic acid butyleneglycol-succinic acid butyleneglycol) the ester P1 used in tri-block copolyester TP1 prepared by the PLLA used in poly(lactic acid)-polyester composite above-described embodiment and comparative example prepared and embodiment 1, the step (1) of embodiment 1 and embodiment 1 makes melting compressing tablet respectively, and the press sheet compression made is carried out Mechanics Performance Testing and biodegradability test.Particularly, the tensile mechanical properties of these press sheet compressions is detected according to GB/T1040.2-2006 method 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 before accounting for test with the press sheet compression after test relative to the mass loss of the press sheet compression before test, the weight percent of press sheet compression represents biological degradation rate.
Detected result is as shown in table 1 below.
Table 1
NB refers to that punching constantly.
According to the data that above-mentioned table 1 is recorded, the press sheet compression made by the press sheet compression made by the poly(lactic acid)-polyester composite prepared as can be seen from embodiment 1 and the poly(lactic acid)-polyester composite prepared by comparative example 1 and 2 is compared, the erosion-resisting characteristics of the press sheet compression that the poly(lactic acid)-polyester composite prepared by embodiment 1 is made and tensile property are all better, show good comprehensive mechanical property; Compared with the press sheet compression be made up of PLLA and P1 by the press sheet compression that the poly(lactic acid)-polyester composite prepared as can be seen from embodiment 1 is made, the toughness (as tensile property) that poly(lactic acid)-polyester composite according to the present invention has clear improvement relative to poly(lactic acid) tool, relative to the rigidity (as resistance to impact shock) that linearly random aliphatic aromatic copolyesters tool has clear improvement.As can be seen here, poly(lactic acid)-polyester composite according to the present invention has preferably comprehensive mechanical property.
And be 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 (11)
1. poly(lactic acid)-polyester composite, this matrix material contains poly(lactic acid), linearly random aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide, wherein, the structural formula of described tri-block copolyester as shown in Equation 1:
Wherein, p is the integer of 5-200, and q is the integer of 5-200, and M comprises the structural unit as shown in following formula 2 and formula 3,
Wherein, Ar is the group with phenyl ring, naphthalene nucleus or anthracene nucleus; M is the integer of 1-20, and n is the integer of 1-16, and t is the integer of 1-20;
The mol ratio of the structural unit shown in formula 2 and formula 3 is the weight-average molecular weight of 1:0.1-10, M section is 6000-600,000, and the weight-average molecular weight of described tri-block copolyester is 10,000-1,000,000;
Described linearly random aliphatic aromatic copolyesters 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, and c is the integer of 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 described linearly random aliphatic aromatic copolyesters is 100,000-600,000, molecular weight distribution index is 1.2-3;
Described organo-peroxide is at least one in dialkyl, diacyl peroxides and peroxyester.
2. matrix material according to claim 1, wherein, with the gross weight of described poly(lactic acid)-polyester composite for benchmark, the content of described poly(lactic acid) is 10-90 % by weight; The content of described linearly random aliphatic aromatic copolyesters is 5-70 % by weight; The content of described tri-block copolyester is 1-20 % by weight; The content of described organo-peroxide is 0.01-1 % by weight.
3. matrix material according to claim 2, wherein, the content of described poly(lactic acid) is 50-70 % by weight; The content of described linearly random aliphatic aromatic copolyesters 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.
4. according to the matrix material in claim 1-3 described in any one, wherein, in formula 1, p is the integer of 10-100, and q is the integer of 10-100; In formula 2, m is the integer of 2-10, and n is the integer of 2-8; In formula 3, t is the integer of 2-10; The mol ratio of the structural unit shown in formula 2 and formula 3 is the weight-average molecular weight of 1:0.5-2, M section is 60,000-120,000, and the weight-average molecular weight of described tri-block copolyester is 80,000-600,000.
5. according to the matrix material in claim 1-3 described in any one, wherein, Ar is following aryl:
Wherein, R
1, R
2, R
3, R
4, R
5and R
6be hydrogen, the alkyl of C1-C4, F, Cl ,-NO independently of one another
2,-CN or-OR
7, wherein, R
7for the alkyl of C1-C4.
6. according to the matrix material in claim 1-3 described in any one, wherein, the weight-average molecular weight of described poly(lactic acid) is 80,000-200,000.
7. according to the matrix material in claim 1-3 described in any one, wherein, in formula 4, a is the integer of 2-4, and b is the integer of 2-4, and c is the integer of 2-4, and d is the integer of 1-3, and e is the integer of 1-2.
8. according to the matrix material in claim 1-3 described in any one, wherein, the weight-average molecular weight of described linearly random aliphatic aromatic copolyesters is 100,000-300,000, and molecular weight distribution index is 1.5-2.5.
9. matrix material according to claim 1, wherein, described organo-peroxide is dicumyl peroxide, 2, at least one in 5-dimethyl-2,5-two (tert-butyl peroxide) hexane, two (tert-butylperoxyiso-propyl) benzene, dibenzoyl peroxide, lauroyl peroxide and tert-butyl hydroperoxide isobutyrate.
10. the preparation method of the poly(lactic acid)-polyester composite in claim 1-9 described in any one, the method comprises: poly(lactic acid), aliphatic aromatic copolyesters, tri-block copolyester and organo-peroxide are mixed, and the mixture obtained is carried out extruding pelletization.
11. poly(lactic acid)-the polyester composites prepared by method according to claim 10.
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