CN101098932B - Biologically-degradable polyester mixture - Google Patents

Biologically-degradable polyester mixture Download PDF

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CN101098932B
CN101098932B CN2005800464749A CN200580046474A CN101098932B CN 101098932 B CN101098932 B CN 101098932B CN 2005800464749 A CN2005800464749 A CN 2005800464749A CN 200580046474 A CN200580046474 A CN 200580046474A CN 101098932 B CN101098932 B CN 101098932B
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mixture
acid
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CN101098932A (en
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U·泽利格
G·斯库平
D·施特克
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BASF SE
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BASF SE
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Abstract

The invention relates to biologically-degradable polyester mixtures, comprising i) 5 to 80 wt. %, based on the total weight of the components i to ii, of a least one polyester made from aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds and ii) 20 to 95 wt. %, based on the total weight of components i to ii, of at least one biologically-degradable homo- or co-polyester, selected from the group comprising polylactides, polycaprolactones, polyhydroxyalkanoates and polyesters made from aliphatic dicarboxylic acids and aliphatic diols and iii) 0.1 to 15 wt. %, based on the total weight of components i to ii, a) of an epoxide-containing copolymer made from styrol, acrylate ester and/or methacrylate ester, b) of a biphenol-A-epoxide or c) an epoxide-containing natural oil, fatty acid ester or fatty acid amide and iv) 0 to 15 wt. % additive and v) 0 to 50 wt. % inorganic or organic fillers and method for production and use thereof.

Description

Biologically-degradable polyester mixture
The present invention relates to comprise the biologically-degradable polyester mixture of following component:
I) based on the gross weight of component i-ii, 5-90 weight % is at least a based on aliphatic series and aromatic dicarboxylic acid with based on the polyester of aliphatic dihydroxy compound;
Ii) based on the gross weight of component i-ii, at least a equal polyester of 10-95 weight % or copolyesters, described equal polyester or copolyesters are selected from polylactide (PLA), polycaprolactone, polyhydroxyalkanoatefrom (as PHB or PHB/V) and comprise aliphatic dicarboxylic acid and the polyester that comprises aliphatic diol;
Iii) based on the gross weight of component i-ii, 0.1-15 weight %a) contain the multipolymer of epoxy group(ing) and styrene-based, acrylate and/or methacrylic ester, b) bisphenol A epoxide, or c) fatty acid amide or fatty acid ester or contain the natural oil of epoxy group(ing); And
Iv) 0-15 weight % additive, for example stablizer, nucleator, lubricant and anti, wax, softening agent, tensio-active agent, static inhibitor, antifogging agent, or dyestuff;
The v) inorganic or organic filler of 0-50 weight %, for example chalk, talcum, silicate, kaolin, mica, wollastonite, polynite, or comprise cellulosic fiber as cotton, flax, hemp, bichu fibre, or the like.
The invention further relates to the method for preparing biologically-degradable polyester mixture, the branching agent masterbatch that helps to prepare polyester mixture of the present invention that can be favourable, the biodegradable polyester mixture is used to prepare the purposes of moulded product, paper tinsel or fiber, and the moulded product, paper tinsel or the fiber that comprise biologically-degradable polyester mixture.
The biodegradable mixture that comprises following component is known (seeing EP-B 792 309): the i) polyester material of synthetic preparation and ii) be selected from polylactide, polycaprolactone, polyhydroxyalkanoatefrom and comprise aliphatic dicarboxylic acid and comprise the equal polyester or the copolyesters of the polyester of aliphatic diol.Ideally, these mixtures combine the desired properties of each component, for example processing that synthesizing polyester is usually good and mechanical property and the availability of relatively low cost usually, and above listed polymer i i) as polylactide, polycaprolactone, polyhydroxyalkanoatefrom with comprise aliphatic dicarboxylic acid and preparation of the polyester environmentally safe ground of aliphatic diol and processing.
Yet the combination that reaches desired properties is in practice had any problem usually.Polylactide and polyhydroxyalkanoatefrom need the predrying to prevent the degraded of polymkeric substance of complexity.Especially in paper tinsel was used, mixture had inadequate bubble stability.This is particularly useful for having the mixture greater than 20% polylactide or polyhydroxyalkanoatefrom and＜80% aromatic-aliphatic copolyesters.In addition, the thick film of especially being made by the mixture of prior art has inadequate paracentesis resistance.This especially betides under the situation of the thick film that mainly comprises polylactide or polyhydroxycarboxyliacid acid.
Therefore, the purpose of this invention is to provide the biodegradable mixture that comprises following component: the i) polyester material of synthetic preparation and ii) be selected from polylactide, polycaprolactone, polyhydroxyalkanoatefrom and comprise aliphatic dicarboxylic acid and comprise the equal polyester or the copolyesters of the polyester of aliphatic diol, these materials do not have above-mentioned shortcoming.
This purpose by beginning definition and below in greater detail biologically-degradable polyester mixture realize.Polyester mixture of the present invention is different from those of prior art, and especially (component iii) by branching agent.
In principle, any conduct half aromatic polyester is known based on aliphatic series and aromatic dicarboxylic acid with can be used as component i based on the polyester of aliphatic dihydroxy compound and be used to prepare biologically-degradable polyester mixture of the present invention.Certainly the mixture of two or more these polyester also is suitable as component i.
According to the present invention, term half aromatic polyester also should comprise polyester derivatives such as polyether ester, polyesteramide or polyether ester amides.Wherein half aromatic polyester of Shi Heing is a linear non-chain extension polyester (WO92/09654).Half aromatic polyester of preferred chain extension and/or branching.The latter is described in the WO 96/15173-15176 that at first mentions, 21689-21692, and 25446,25448, in WO 98/12242 specification sheets, specially be incorporated herein by reference at this.Also can use the mixture of different half aromatic polyesters.Term half aromatic polyester especially should refer to for example Ecoflex of product
Figure G05846474920070716D000021
(BASF Aktiengesellschaft) and Eastar Bio (Novamont).
Wherein particularly preferred half aromatic polyester is the polyester that comprises following important component:
A) comprise the acid constituents of following component:
A1) at least a aliphatic dicarboxylic acid of 30-99 mole %, or at least a cycloaliphatic dicarboxylic acid or its become ester derivative, or these mixture,
A2) at least a aromatic dicarboxylic acid of 1-70 mole %, or its one-tenth ester derivative, or these mixture, and
A3) 0-5 mole % comprises the compound of sulfonate group;
B) be selected from least a C 2-C 12Alkanediol and at least a C 5-C 10The diol component of cycloalkanes glycol, or these mixture;
And one or more are selected from the component of following component if necessary:
C) be selected from the component of following component:
C1) at least a dihydroxy compound that comprises ether official energy and have formula I:
HO-[(CH 2) n-O] m-H (I)
Wherein n be 2,3 or 4 and m be the integer of 2-250,
C2) hydroxycarboxylic acid of at least a formula IIa or IIb:
Figure G05846474920070716D000031
Wherein p is the integer of 1-1500, and r is the integer of 1-4, G for be selected from phenylene ,-(CH 2) q-,-C (R) H-and-C (R) HCH 2Group, wherein q is the integer of 1-5, R is methyl or ethyl,
C3) at least a amino-C 2-C 12Alkanol, or at least a amino-C 5-C 10Cycloalkanol, or these mixture,
C4) at least a diamino-C 1-C 8Alkane,
C5) 2 of at least a formula III, 2 '-bisoxazolines:
Figure G05846474920070716D000032
R wherein 1Be singly-bound, (CH 2) z-alkylidene group or phenylene, z=2,3 or 4 wherein,
C6) at least aly be selected from naturally occurring amino acid, by dicarboxylic acid with 4-6 carbon atom and the available polymeric amide of diamines polycondensation with 4-10 carbon atom, the aminocarboxylic acid of the compound of formula IVa and IVb:
Figure G05846474920070716D000033
Wherein s is the integer of 1-1500, and t is the integer of 1-4, T for be selected from phenylene ,-(CH 2) u-,-C (R 2) H-and-C (R 2) HCH 2-group, wherein u is the integer of 1-12, R 2Be methyl or ethyl,
And have repeating unit V De Ju oxazoline:
Figure G05846474920070716D000041
R wherein 3Be hydrogen, C 1-C 6Alkyl, C 5-C 8Cycloalkyl, unsubstituted or have three C at the most 1-C 4The phenyl of alkyl substituent, or tetrahydrofuran base,
Or comprise c1)-c6) mixture;
And
D) be selected from the component of following component:
D1) at least a compounds with at least three one-tenth ester groups,
D2) at least a isocyanic ester and
D3) at least a divinyl ether,
Or comprise d1)-d3) mixture.
In a preferred embodiment, the acid constituents A of half aromatic polyester comprises 30-70 mole %, especially 40-60 mole %a1 and 30-70 mole %, especially 40-60 mole %a2.
Spendable aliphatic acid and corresponding derivative a1 are generally has 2-10 carbon atom, those of preferred 4-6 carbon atom.They can be for linearity or branching.The cycloaliphatic dicarboxylic acid who can be used for the object of the invention is generally those with 7-10 carbon atom, and especially has 8 carbon atoms those.Yet, also can use carbon atom in principle as having the dicarboxylic acid of 30 carbon atoms at the most with bigger number.
The example that can mention is: propanedioic acid, succsinic acid, pentanedioic acid, 2-methylglutaric acid, 3-methylglutaric acid, hexanodioic acid, pimelic acid, nonane diacid, sebacic acid, fumaric acid, 2,2-dimethylated pentanedioic acid, suberic acid, 1,3-pentamethylene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, diglycollic acid, methylene-succinic acid, toxilic acid and 2,5-norcamphane dicarboxylic acid.
The above-mentioned aliphatic series that also can use and can mention or cycloaliphatic dicarboxylic acid's one-tenth ester derivative be two-C especially 1-C 6Alkyl ester such as dimethyl esters, diethyl ester, di ester, diisopropyl ester, di-n-butyl ester, diisobutyl ester, di-t-butyl ester, two n-pentyl esters, diisoamyl ester or di-n-hexyl ester.Also can use the acid anhydride of dicarboxylic acid.
Dicarboxylic acid or its become ester derivative can use separately here or to comprise two or more these dicarboxylic acid or it becomes the form of the mixture of ester derivative to use.
Preferred use succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, brassylic acid, or its one-tenth ester derivative separately, or these mixture.Especially preferably use succsinic acid, hexanodioic acid or sebacic acid, or its one-tenth ester derivative separately, or these mixture.Especially preferably use hexanodioic acid or its to become ester derivative such as its alkyl ester, or these mixture.When preparation has the component polymeric blends ii) of " firmly " or " crisp ", poly butyric ester or especially during polylactide, the mixture that preferably uses sebacic acid or sebacic acid and hexanodioic acid is as aliphatic dicarboxylic acid for example.When preparation has the component polymeric blends ii) of " soft " or " firmly ", for example during poly butyric ester-altogether-valerate, the mixture that preferably uses succsinic acid or succsinic acid and hexanodioic acid is as aliphatic dicarboxylic acid.
Succsinic acid, nonane diacid, sebacic acid and brassylic acid additionally have the advantage that can obtain with the form of renewable raw materials.
The aromatic dicarboxylic acid a2 that can mention is generally those with 8-12 carbon atom, preferably has those of 8 carbon atoms.For example, can mention terephthalic acid, m-phthalic acid, 2,6-naphthoic acid and 1,5-naphthoic acid and one-tenth ester derivative thereof.Here can should be mentioned that two-C especially 1-C 6Alkyl ester such as dimethyl esters, diethyl ester, di ester, diisopropyl ester, di-n-butyl ester, diisobutyl ester, di-t-butyl ester, two n-pentyl esters, diisoamyl ester or di-n-hexyl ester.The acid anhydride of dicarboxylic acid a2 is the one-tenth ester derivative for being fit to also.
Yet, also can use carbon atom in principle as reaching the aromatic dicarboxylic acid a2 of 20 carbon atoms with bigger number.
The one-tenth ester derivative of aromatic dicarboxylic acid or these a2 can use separately or become the mixture of ester derivative to use as two or more these aromatic dicarboxylic acids or its.Especially preferably use terephthalic acid or its to become ester derivative such as dimethyl terephthalate (DMT).
The used compound that comprises sulfonate group is generally dicarboxylic acid or one of its basic metal that becomes ester derivative or the alkaline earth salt that contains sulfonate radical, an alkali metal salt or its mixture of preferred 5-sulfoisophthalic acid, special particular certain cancers.
In a preferred embodiment, acid constituents A comprises 40-60 mole %a1,40-60 mole % a2 and 0-2 mole %a3.In a further preferred embodiment, acid constituents A comprises 40-59.9 mole %a1,40-59.9 mole %a2 and 0.1-1 mole %a3, especially 40-59.8 mole %a1,40-59.8 mole %a2 and 0.2-0.5 mole %a3.
Glycol B is selected from usually has 2-12 carbon atom, the branching or the linear alkanediol of preferred 4-6 carbon atom, or be selected from cycloalkanes glycol with 5-10 carbon atom.
The example of the alkanediol that is fit to is an ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 2,4-dimethyl-2-ethyl-1,3-hexylene glycol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol and 2,2,4-trimethylammonium-1,6-hexylene glycol, especially ethylene glycol, 1, ammediol, 1,4-butyleneglycol or 2 (neopentyl glycol); Ring pentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol or 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Preferred especially 1, the 4-butyleneglycol, especially with the hexanodioic acid combination as component a1) and 1, ammediol, especially with the sebacic acid combination as component a1).1, ammediol and 1,4-butyleneglycol additionally have the advantage that can obtain with the form of renewable raw materials.Also can use the mixture of different alkanediols.
Whether depend on needs excessive acidic group or OH end group, component A or B component can excessively be used.In a preferred embodiment, the mol ratio of used component A and B component can be 0.4: 1-1.5: 1, preferred 0.6: 1-1.1: 1.
Except that component A and B, polyester mixture of the present invention based on polyester can comprise other components.
The preferred dihydroxy compound c1 that uses is glycol ether, triglycol, polyoxyethylene glycol, polypropylene glycol and polytetrahydrofuran (poly-THF), preferred especially glycol ether, triglycol and polyoxyethylene glycol, also can use these mixture, having different variable n (seeing formula I) can be by the known polymerization process of use itself, and at first with the ethylene oxide polymerization, the compound that obtains with the propylene oxide polymerization then, the polyoxyethylene glycol that for example comprises propylene units (n=3), be preferably based on the polymkeric substance of the polyoxyethylene glycol with different variable n especially, wherein the unit that is formed by ethylene oxide accounts for leading.The molar mass M of polyoxyethylene glycol n) usually at 250-8000g/mol, select in the preferred 600-3000g/mol scope.
In a preferred embodiment of preparation half aromatic polyester, for example can use molar weight, 15-98 mole %, preferred 60-99.5 mole % glycol B and 0.2-85 mole %, preferred 0.5-30 mole % dihydroxy compound c1 based on B and c1.
In a preferred embodiment, be used to prepare the hydroxycarboxylic acid c2 of half aromatic polyester) be: oxyacetic acid, D-, L-or D, L-lactic acid, 6 hydroxycaproic acid, or its cyclic derivatives such as glycollide (1,4-diox-2,5-diketone), D-or L-dilactide (3,6-dimethyl-1,4-diox-2,5-diketone), P-hydroxybenzoic acid, or its oligopolymer and polymkeric substance as poly-3-hydroxybutyric acid, poly-hydroxypentanoic acid, polylactide (for example with NatureWorks (Cargill) form is available), or the mixture of poly-3-hydroxybutyric acid and poly-hydroxypentanoic acid (latter is as from the Biopol of Zeneca
Figure G05846474920070716D000072
Can obtain), preferred especially its lower molecular weight and cyclic derivatives.
The example of the amount of available hydroxycarboxylic acid is the amount 0.01-50 weight % based on A and B, preferred 0.1-40 weight %.
Be used for amino-C of the present invention 2-C 12Alkanol or amino-C 5-C 10Cycloalkanol (amount of component b 3) also comprises 4-amino methyl cyclohexane methanol, preferred amino-C 2-C 6Alkanol such as 2-monoethanolamine, amino amylalcohol of 3-aminopropanol, 4-amino butanol, 5-or 6-amino-hexanol, or amino-C 5-C 6The pure and mild Trans-4-Amino Cyclohexanol of cycloalkanol such as amino cyclopentyl, or these mixture.
Used diamino-C 1-C 8Preferred diamino-the C of alkane (amount of component b 4) 4-C 6Alkane is as 1,4-diaminobutane, 1,5-diamino pentane or 1 (hexamethylene-diamine, " HMD ").
In a preferred embodiment of preparation half aromatic polyester, use molar weight 0.5-99.5 mole %, preferred 0.5-50 mole %c3 and based on the molar weight 0-50 mole % of B, preferred 0-35 mole %c4 based on B.
2 of formula III, 2 '-bisoxazoline c5 are usually by Angew.Chem.Int.Edit., and the 11st rolls up (1972), and the method for 287-288 page or leaf can obtain.Particularly preferred bisoxazoline is R wherein 1Be singly-bound, (CH 2) zAlkylidene group, wherein z=2,3 or 4 is as methylene radical, ethane-1,2-two bases, propane-1,3-two bases or propane-1,2-two bases, or those of phenylene.The particularly preferred bisoxazoline that can mention is 2,2 '-two (2-oxazolines), two (2-oxazolinyl) methane, 1, two (2-oxazolinyl) ethane, 1 of 2-, two (2-oxazolinyl) propane and 1 of 3-, two (2-oxazolinyl) butane of 4-, especially 1, two (2-oxazolinyl) benzene, 1 of 4-, two (2-oxazolinyl) benzene or 1 of 2-, two (2-oxazolinyl) benzene of 3-.
In preparation half aromatic polyester, for example can use under every kind of situation total molar weight 70-98 mole %B, at the most 30 moles of %c3 and 0.5-30 mole %c4 and 0.5-30 mole %c5 based on B component, c3, c4 and c5.In other preferred embodiment, use gross weight 0.1-5 weight %, preferred 0.2-4 weight %c5 based on A and B.
Component utilized c6 can be naturally occurring aminocarboxylic acid.These comprise Xie Ansuan, L-LEU, L-iLeu, Threonine, methionine(Met), phenylalanine, tryptophane, Methionin, L-Ala, arginine, aspartic acid, halfcystine, L-glutamic acid, glycine, Histidine, proline(Pro), Serine, tyrosine, l-asparagine and glutamine.
The aminocarboxylic acid of preferred formula IVa and IVb is that s is the integer of 1-1000, and t is the integer of 1-4, preferred 1 or 2 and T be selected from phenylene and-(CH 2) u-, wherein u is those of 1,5 or 12.
C6 also can be the poly-oxazoline of formula V.Yet c6 also can be the mixture of different aminocarboxylic acids and/or poly-oxazoline.
In a preferred embodiment, the amount of used c6 is the total amount 0.01-50 weight % based on component A and B, preferred 0.1-40 weight %.
Can use the component that is used for preparing half aromatic polyester if necessary at other, for comprising at least three compound d 1 that can become ester group.
Compound d 1 preferably comprises 3-10 the functional group that can form ester bond.Particularly preferred compound d 1 has 3-6 such functional group, especially 3-6 hydroxyl and/or carboxyl in molecule.The example that should mention is as follows: tartrate, citric acid, toxilic acid; TriMethylolPropane(TMP), trimethylolethane; Tetramethylolmethane; Polyether triol; Glycerine; Trimesic acid; Trimellitic acid, trimellitic acid 1,2-anhydride; Pyromellitic acid, pyromellitic dianhydride and hydroxyl m-phthalic acid.
Compound d 1 common used amount is based on component A, 0.01-15 mole %, preferred 0.05-10 mole %, preferred especially 0.1-4 mole %.
Component utilized d2 is the mixture of isocyanic ester or different isocyanic ester.For example can use aromatics or aliphatic vulcabond.Yet also can use the more isocyanic ester of high functionality.
For the present invention, aromatic diisocyanate especially is a toluene 2,4-vulcabond, toluene 2,6-vulcabond, ditan 2,2 '-vulcabond, ditan 2,4 '-vulcabond, ditan 4,4 '-vulcabond, naphthylidene 1,5-vulcabond or xylylene diisocyanate.
In these isocyanic ester, preferred especially ditan 2,2 '-, 2,4 '-and 4,4 '-vulcabond is as component d2.The latter's vulcabond uses as mixture usually.
Also spendable three ring isocyanic ester d2 are three (4-isocyano-phenyl) methane.The polycyclic aromatic vulcabond for example comes across in the preparation of monocycle or dicyclo vulcabond.
Component d2 also can comprise the gross weight based on component d2, and auxiliary quantity is 5 weight % urea diketone (uretdione) groups at the most for example, for example are used for blocked isocyanate groups.
For the present invention, aliphatic vulcabond d2 is mainly has 2-20 carbon atom, the linearity of preferred 3-12 carbon atom or sub-branched alkyl vulcabond or ring alkylidene group vulcabond, for example hexa-methylene 1,6-vulcabond, isophorone diisocyanate or methylene-bis (4-isocyanato hexanaphthene).Hexa-methylene 1,6-vulcabond and isophorone diisocyanate are particularly preferred aliphatic vulcabond d2.
Preferred isocyanuric acid ester is for being derived from C 2-C 20, preferred C 3-C 12The aliphatic isocyanuric acid ester of ring alkylidene group vulcabond or alkylidene group vulcabond such as isophorone diisocyanate or methylene-bis (4-isocyanato hexanaphthene).What the alkylidene group vulcabond can be for linearity or branching here.Be preferably based on the isocyanuric acid ester of positive hexamethylene diisocyanate especially, for example cyclic trimer, pentamer or the higher oligomer of positive hexamethylene diisocyanate.
Based on the integral molar quantity of A and B, the amount of component utilized d2 is 0.01-5 mole % usually, preferred 0.05-4 mole %, preferred especially 0.1-4 mole %.
Spendable divinyl ether d3 is generally any routine and commercially available divinyl ether.Preferred use 1,4-butyleneglycol divinyl ether, 1,6-hexylene glycol divinyl ether or 1,4 cyclohexane dimethanol divinyl ether or its mixture.
Based on the gross weight of A and B, preferably the amount of the divinyl ether that uses is 0.01-5 weight %, especially 0.2-4 weight %.
The example of preferred half aromatic polyester is based on following component:
A、B、d1；
A、B、d2；
A、B、d1、d2；
A、B、d3；
A、B、c1；
A、B、c1、d3；
A、B、c3、c4；
A、B、c3、c4、c5；
A、B、d1、c3、c5；
A、B、c3、d3；
A、B、c3、d1；
A、B、c1、c3、d3；
A、B、c2。
In these half aromatic polyesters, be preferably based on A, B and d1 especially, or A, B and d2, or half aromatic polyester of A, B, d1 and d2.In a further preferred embodiment, half aromatic polyester is based on A, B, c3, c4 and c5 or A, B, d1, c3 and c5.
Half aromatic polyester and the polyester mixture of the present invention mentioned are generally biodegradable.
For the present invention, at DIN V 54900-2 (first grade standard, in September, 1998) Ding Yi three kinds of methods one of at least in, if the biodegradable gon of the mixture of material or material is at least 60%, the mixture of then this material or material is observed the feature term " biodegradable " ".
Because biodegradable, polyester or polyester mixture usually during suitable and demonstrable in destruction.But degraded enzymatic, hydrolysis, oxidation and/or by being exposed to generation electromagnetic radiation such as UV radiation under, and major part mainly causes by being exposed under microorganism such as bacterium, yeast, fungi and the algae.The example of method that quantizes biodegradable is for making polyester and mix with compost and store specified time.For example according to DIN EN 13432 or DIN V 54900-2, method 3 makes no CO in composting waste material process 2Air by the compost of slaking and the temperature variation that makes compost stand to stipulate.Here biodegradable is by CO that sample discharged 2Clean amount (deduct the CO that no sample compost is discharged 2Amount after) CO that discharged with sample 2The ratio of possible maximum (calculating) by the carbon content of sample measure, this is than being defined as biodegradable per-cent.Even at the composting waste material after several days, Biodegradable polyester or biologically-degradable polyester mixture demonstrate tangible signs of degradation usually, for example fungal growth, track and eyelet.
The additive method of measuring biodegradable for example is described in ASTM D5338 and ASTMD6400.
The preparation of half aromatic polyester itself is knownly maybe can be undertaken by known method itself.
Preferred half aromatic polyester is characterised in that molar mass (M n) be 1000-100 000g/mol, preferred 10 000-50 000g/mol of 9000-75 000g/mol especially, fusing point is 60-170 ℃, preferred 80-150 ℃.
Half aromatic polyester of mentioning can have hydroxyl and/or carboxyl end group with any required ratio.Half aromatic polyester of mentioning also can be for terminal groups modification.For example the OH end group can be by carrying out sour modification with phthalic acid, phthalate anhydride, trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic acid or pyromellitic acid anhydride reactant.
In principle, the component ii that is fit to of biologically-degradable polyester mixture is selected from polylactide, polycaprolactone, polyhydroxyalkanoatefrom and comprises aliphatic dicarboxylic acid and comprise the equal polyester or the copolyesters of the polyester of aliphatic diol.Preferred ingredients ii is polylactide (PLA) and polyhydroxyalkanoatefrom, and poly butyric ester (PHB) and poly butyric ester-altogether-valerate (PHBV) especially here.Especially product, for example NatureWorks in these materials
Figure G05846474920070716D000111
(from the polylactide of Cargill Dow), Biocycle
Figure G05846474920070716D000112
(from the poly butyric ester of PHB Ind.); Enmat
Figure G05846474920070716D000113
(from poly butyric ester-common-valerate of Tianan).
Component iii of the present invention comprises the multipolymer that a) contains epoxy group(ing) and styrene-based, acrylate and/or methacrylic ester, b) bisphenol A epoxide, or c) fatty acid amide or fatty acid ester or contain the natural oil of epoxy group(ing).
The preferred multipolymer that contains epoxy group(ing) and styrene-based, acrylate and/or methacrylic ester that uses.Compound has two or more epoxy group(ing) usually in molecule.Oligomeric or the polymeric rings oxygen compound is especially suitable, example is 2-glycidyl ester or many glycidyl ester of dicarboxylic acid or polycarboxylic acid, or the 2-glycidyl ester of glycol or polyvalent alcohol or many glycidyl esters, or comprise the multipolymer of vinylbenzene and (methyl) glycidyl acrylate, for example as Joncryl
Figure G05846474920070716D000114
ADR 4368 trade marks are commercially available by JohnsonPolymer.Other preferred ingredients iii is that molecule comprises at least one carbon-to-carbon double bond or triple bond and comprises the compound of at least one epoxy group(ing).What especially be fit to is glycidyl acrylate and glycidyl methacrylate.
Preferred in addition c) fatty acid ester or (epoxidised) naturally occurring oil of containing epoxy group(ing) are as component iii).The example of naturally occurring oil is the mixture of sweet oil, Toenol 1140, soybean oil, plam oil, peanut oil, Oleum Cocois, algal oil, Oils,glyceridic,cod-liver or these compounds.Preferred especially epoxidised soybean oil (for example from Hobum, the Merginat of Hamburg ESBO or from Cognis, the Edenol of D ü sseldorf
Figure G05846474920070716D000116
B 316).Special preferred structure type a) and c) combination is as component iii.As more detailed description among the embodiment, preferred especially Joncryl
Figure G05846474920070716D000117
ADR 4368 (structure type a)) and Merginat
Figure G05846474920070716D000118
ESBO (structure type c)) combination.
Used component amount iii) is based on component i)-ii) gross weight 0.1-15 weight %, preferred 0.1-10 weight %, preferred especially 0.5-2 weight %.
Biologically-degradable polyester mixture of the present invention comprises 5-90 weight % usually, preferred 10-85 weight %, preferred especially 15-80 weight %, especially 40-60 weight % component i and 10-95 weight %, preferred 20-80 weight %, preferred especially 40-80 weight %, 40-60 weight % component ii very particularly preferably, wherein wt per-cent is 100 weight % based on gross weight and the summation of component i-ii always.
In a preferred embodiment of the invention, component i forms external phase or common external phase, and preferred ingredient i forms external phase.
With regard to preparation extrusioning thermoplastic plastic such as paper tinsel, bubble stability is very important.Found that now wherein component i forms preferred external phase or at least a external phase, and the mixture that component ii has inserted this phase at isolated area has good bubble stability.For making component i form external phase, mixture has usually greater than 40 weight %, is preferably greater than 50 weight % component i, under every kind of situation based on the gross weight of component i and ii.
With regard to preparation moulded product such as injection molding, can use to have high poly butyric ester (PHB) content or especially high polylactide (PLA) content (component polyester mixture ii).Here can use mixture usually with 60-95 weight % component.The shock-resistant moulded product method for compositions of improved preparation is described in the preparation method.
If comprise sebacic acid (component a1)) or the polyester of mixture that comprises sebacic acid and hexanodioic acid as component i), then with component mixture ii) in amount of polyester in fact even can be low to moderate 10 weight % with smallest limit.
In addition, biologically-degradable polyester mixture of the present invention comprises 0.1-15 weight % usually, preferred 0.1-10 weight %, preferred especially 0.5-5 weight % component iii, wherein under every kind of situation weight percent based on the gross weight of component i-ii.
Biologically-degradable polyester mixture of the present invention can comprise other additives well known by persons skilled in the art.Concrete additive is stablizer, nucleator, lubricant and anti such as stearate (especially calcium stearate), wax such as beeswax or beeswax ester; Softening agent such as citrate (especially Tributyl O-acetylcitrate), glyceryl ester such as triacetyl glycerine, or glycol derivative; Tensio-active agent such as polysorbate, cetylate, laurate; Static inhibitor, antifogging agent or dyestuff.The concentration of used additive is based on polyester mixture 0-15 weight %, especially 1-10 weight % of the present invention.
Mineral filler or organic filler that spendable filler is mentioned for beginning.The concentration of used filler is based on polyester mixture 0-50 weight %, especially 1-10 weight % of the present invention.
Biologically-degradable polyester mixture of the present invention can pass through currently known methods (EP 792 309 and US5,883,199) by each component preparation.
For example, can in a processing step, all component i, ii and mixed being incorporated in mixing device well known by persons skilled in the art such as kneader or the forcing machine of iii be reacted down as 120 ℃-250 ℃ in the temperature that raises.Reaction is preferably carried out in the presence of radical initiator.
In addition, found a kind of improving one's methods of biologically-degradable polyester mixture of the present invention that prepare.
For this reason, with 1-50 weight %, preferred 5-35 weight % component iii and 50-99 weight %, preferred 65-95 weight % component i are at 110-145 ℃ in first step, and preferred 120-140 ℃ is mixed to obtain the branching agent masterbatch down.Under these temperature, obtain uniform blend, molecular weight does not obviously improve.The branching agent masterbatch that obtains can easily at room temperature be stored.In second step, if required composition can be set up by the branching agent masterbatch being added component ii and being fit to add among the other component i.This compounding step is at 150-250 ℃, carries out under preferred 160-190 ℃.
Temperature in the compounding step can be selected from zn cpds, tin compound and titanium compound and C by use usually 1-C 12Therefore the activator of alkyl triphenyl phosphonium halide and reducing avoids responsive biological polymer such as poly butyric ester to decompose.
Typical branching agent masterbatch comprises 5-35 weight %, preferred 10-20 weight % component iii) with 65-95 weight %, preferred 80-90 weight % component i.Surprisingly, when when comprising component and ii) comparing, proving that these branching agent masterbatch are favourable with branching agent masterbatch iii) with corresponding.The branching agent masterbatch is by the invention provides.Among the embodiment 4-6 that lists from following later phases, obviously the present invention comprises component i) and the branching agent masterbatch that can buy usually (as polylactide and glycidyl methacrylate) of flow rate compare with to(for) the polyester mixture of formation of branching agent masterbatch iii) be favourable.Branching agent masterbatch of the present invention also has the feature of fabulous package stability.
The example of branching agent masterbatch of the present invention is:
Component i), the polyester for preparing by following component condensation:
Hexanodioic acid/terephthalic acid and 1,4-butyleneglycol (Ecoflex for example
Figure G05846474920070716D000131
FBX 7011);
Hexanodioic acid/terephthalic acid and 1, ammediol;
Succsinic acid/terephthalic acid and 1, the 4-butyleneglycol;
Succsinic acid/terephthalic acid and 1, ammediol;
Sebacic acid/terephthalic acid and 1, the 4-butyleneglycol;
Sebacic acid/terephthalic acid and 1, ammediol;
Nonane diacid/terephthalic acid and 1, the 4-butyleneglycol;
Brassylic acid/terephthalic acid and 1, the 4-butyleneglycol; With
Component is iii): glycidyl-vinylbenzene (methyl) acrylate copolymer is (for example from the Joncryl of JohnsonPolymer
Figure G05846474920070716D000141
ADR 4368).
For preparation has the ii) polyester mixture of content of high " firmly " or " crisp " component, for example＞50 weight % poly butyric ester or especially polylactide, following program certification is particularly advantageous.As mentioned above by blending ingredients i) if, ii) and iii) or in two steps by one of above-mentioned branching agent masterbatch and component ii) and suitable other component i) mix and prepare the intermediate compounding material, preferably comprise 48-60 weight %i), 40-50 weight % component ii) with 0.5-2 weight % component iii).In other step, now this intermediate compounding material is ii) handled component content ii) in realizing required polyester mixture with other component.Polyester mixture by this three phase methods preparation has fabulous suitability for the biodegradable shock-resistant polyester mixture of preparation.
When preparation had high " firmly " or " crisp " component ii) as the polymeric blends of poly butyric ester or especially polylactide content, the mixture of sebacic acid or sebacic acid and hexanodioic acid was preferably used as aliphatic dicarboxylic acid.
On with the empirical basis of other compounding materials (for example Ecoflex/ starch material of compounding), the variation scheme is to use expanding material to realize this purpose.Not that expanding material is mixed in the whole matrix with expensive, but the expanding material enriched material modification of only a part of Ecoflex/PLA preparaton.As the known example of expanding material masterbatch is above-mentioned intermediate compounding material and branching agent masterbatch.This has saved the compounding expense:
9.5-89.5 weight %Ecoflex, 89.5-9.5 weight %PLA, 0.5-20 weight % branching agent masterbatch, 0-15 weight % additive (for example cetylate, laurate, stearate, PEG, citrate and/or glycerol derivative) and 0-50 weight % filler (chalk, talcum, kaolin, silica etc.)
29.5-59.5 weight %Ecoflex, 59.5-29.5 weight %PLA, 0.5-20 weight % branching agent masterbatch, 0-15 weight % additive (for example cetylate, laurate, stearate, PEG, citrate and/or glycerol derivative) and 0-50 weight % filler (chalk, talcum, kaolin, silica).
Biologically-degradable polyester mixture of the present invention is particularly suited for preparing moulded product, paper tinsel or fiber.The preparation method can use method known to those skilled in the art.
A special application with biologically-degradable polyester mixture of improved degradation rate relates to and is used to prepare paper tinsel, especially the agricultural cover foil.Lay these cover foil with the main growth of seedlings of protection and promotion field.After the results, these cover foil are stayed the field or are ploughed in the soil under the situation of biodegradable cover foil.But the basic biological degradation of these cover foil must take place before beginning sowing next year.
Can easily process (having bubble stability) to obtain the paper tinsel of puncture by the biodegradable polymers mixture that biologically-degradable polyester mixture of the present invention obtains.
Embodiment
The related application test:
The molecular weight M of half aromatic polyester nMensuration as follows:
15mg half aromatic polyester is dissolved in the 10ml hexafluoroisopropyl alcohol (HFIP).In each case, analyze this solution of 125 μ l by gel permeation chromatography (GPC).At room temperature measure.For elution, use HFIP+0.05 weight % trifluoroacetic acid potassium.Elution speed is 0.5ml/min.Here use the combination as lower prop (all posts are by the Showa Denko Ltd. of company, and Japan produces): Shodex
Figure G05846474920070716D000151
HFIP-800P (diameter 8mm, long 5cm), Shodex
Figure G05846474920070716D000152
HFIP-803 (diameter 8mm, long 30cm), Shodex HFIP-803 (diameter 8mm, long 30cm).Half aromatic polyester detects by RI detector (differential refraction method).Molecular weight M n=505 to M nThe polymethylmethacrylate standard specimen of=2 740 000 narrow distribution is used for calibration.Elution scope beyond this is interval is measured by extrapotation.
The fusing point of half aromatic polyester uses from the ExstarDSC 6200R device of Seiko company and measures by the dsc measurement method:
Heating rate with 20 ℃/min under each comfortable nitrogen of 10-15mg sample is heated to 200 ℃ from-70 ℃.The given fusing point of sample is the peak temperature of the melting peak that observes at this duration of test.In each case, Kong sample crucible is with for referencial use.
The uniformity of mixture of component i, ii and iii and the uniformity of mixture that is used for comparative preparation be by pressing down these mixtures at 190 ℃, and the paper tinsel that obtains thickness under every kind of situation and be 30 μ m is measured.Assessment visually is present in the ratio of the not dispersive component ii in these paper tinsels.
The degradation rate of biologically-degradable polyester mixture and the following mensuration of degradation rate that is used for the mixture of comparative preparation:
At 190 ℃ of mixtures that press down biologically-degradable polyester mixture and be used for comparative preparation, obtain the paper tinsel that thickness is 30 μ m under every kind of situation.These paper tinsels are cut into the square sheets that the length of side is 20cm separately.Measure every weight of these paillon foils and be defined as " 100 weight % ".Paillon foil is placed on the cloth that is full of soil, and around placing in the case with control atmospheric condition, the soil humidity that detects every day is about 40% based on the maximum water-retaining capacity of soil.Keep constant envrionment conditions in the case during around this: 30 ℃ of temperature, relative humidity is about 50%, and the radiation irradiation paper tinsel that produces by the irradiator that Heraeus SUNTEST quickens, and wavelength is 300-800nm, and yield of radiation is 765W/m 2Measure the residuals weight of each paillon foil and calculated weight percentage ratio (measuring and be defined as the weight of " 100 weight % " during based on on-test) again week about.
Starting raw material
Component i:
I-1: be preparation polyester i-1, with 87.3kg dimethyl terephthalate (DMT), 80.3kg hexanodioic acid, 117kg1,4-butyleneglycol and 0.2kg glycerine mix with 0.028kg tetra-butyl orthotitanate (TBOT), and the mol ratio of alkoxide component and acid constituents is 1.30.With reaction mixture be heated to 180 ℃ and under this temperature the reaction 6 hours.Temperature is increased to 240 ℃ then, by under vacuum, removing excessive dihydroxy compound through distillation in 3 hours.In 1 hour, the 0.9kg hexamethylene diisocyanate slowly is being metered under 240 ℃ then.
The polyester i-1 fusing point that obtains is 119 ℃, molar mass (M n) be that 23 000g/mol are (corresponding to the Ecoflex of BASFAktiengesellschaft production
Figure G05846474920070716D000161
FBX 7011).
Component ii:
Ii-1: aliphatic polyester, from the Natureworks of Cargill-Dow
Figure G05846474920070716D000162
The 2000D polylactide.
Component iii:
Iii-1: from the Joncryl of Johnson Polymer
Figure G05846474920070716D000163
ADR 4368.
Iii-2:ESBO: epoxy soybean oil (for example from Hobum, the Merginat of Hamburg
Figure G05846474920070716D000164
ESBO or from Cognis, the Edenol of D ü sseldorf
Figure G05846474920070716D000165
B 316).
Other components:
Additive: erucicamide, ethylenebisstearamide.
Embodiment 1-3)
Figure G05846474920070716D000166
? ? ? ?iii-1 ?
Inventive embodiments 3 54.8 weight % component i-1 44 weight % component ii-1 0.2 weight % Joncryl component iii-1 1 weight % ESBO
The mixture difference of the mixture of inventive embodiments 2 and inventive embodiments 1 is only for adding 0.2 weight % component iii-1 (from the Joncryl of Johnson Polymer ADR 4368).Component iii-1 is the form adding (total amount that adds the branching agent masterbatch in the above mixture only is 1 weight %) that is dispersed in the branching agent masterbatch among the component i-1 of 20 weight % with concentration.The blown film extrusion molding with the process of paper tinsel that obtains thickness and be about 30-40 μ m in, bubble stability and the horizontal anti tear ductility of extruding direction improved by adding component iii.
In inventive embodiments 3, improved the ratio (and reduced component ii ratio) of component i.Formed the external phase of component i.Such paper tinsel has obviously higher bubble stability.
Embodiment Horizontal anti tear ductility Paper tinsel thickness Bubble stability
Inventive embodiments 1 19N/mm 35+7μm Disconnect eyelet, bubble " dancing ", crimping
Inventive embodiments 2 27N/mm 32+7μm Crimping
Inventive embodiments 3 32N/mm 37+4μm Than inventive embodiments 2 crimping still less
By various branching agent masterbatch preparations and test polyester mixture of the present invention, inventive embodiments 4)-6):
Step 1: preparation branching agent masterbatch
The branching agent masterbatch Component i Component ii Component iii
BR-A ? 90% polylactide 10％Joncryl?ADR?4368
BR-B 80％Ecoflex?F ? 20％Joncryl?ADR?4368
BR-C 70％Ecoflex?F ? 30％Joncryl?ADR?4368
Step 2: compounding polyester mixture of the present invention
Compounding is described
Make the mixture that comprises Ecoflex, PLA, lubricant masterbatch and branching agent masterbatch pass BerstorffZE 40, it has following temperature distribution for rotating, have the self-cleaning twin screw extruder of downstream plenum area 9 in the same way:
Form:
Inventive embodiments 4) Ecoflex/PLA
53％?NatureWorks?4042?D
40％?Ecoflex?F?BX?7011
5% based on PLA, has the EBS masterbatch of 10% ethylenebisstearamide
2% BR-A: based on the branching agent masterbatch of PLA
Inventive embodiments 5) Ecoflex/PLA
60％?NatureWorks?4042?D
38％?Ecoflex?F?BX?7011
1% has Ecoflex SL 1 masterbatch of 10% erucicamide
1% BR-B: based on the branching agent masterbatch of Ecoflex
Inventive embodiments 6) Ecoflex/PLA
60％?NatureWorks?4042?D
38％?Ecoflex?F?BX?7011
1% has Ecoflex SL 1 masterbatch of 10% erucicamide
1% BR-C: based on the branching agent masterbatch of Ecoflex
The compounding in ZE 40 of these preparatons.
Be to assess on the lab setup of 60mm in the processing characteristics during the blown film extrusion molding at screw diameter.The blown film mould comprises the helix core rod divider with 8 spirals.Mould diameter is 190mm, and the gap is 1.2mm.In the nip roll temperature is that 160-165 ℃ and die temperature are on 180-185 ℃ the basis of temperature distribution, is external phase owing to have the polylactide of its known low melt strength in the Ecoflex/PLA of compounding material, and paper tinsel has limited overall film bubble stability.
Mechanical measurement obtains following result:
Performance Inventive embodiments 4 Inventive embodiments 5 Inventive embodiments 6
Young's modulus, parallel ?1681MPa ?1632MPa ?1525MPa
Young's modulus is vertical ?1106MPa ?1244MPa ?990MPa
The fracture tension strain, parallel ?326％ ?332％ ?160％
The fracture tension strain, vertical ?102％ ?135％ ?31％
Horizontal anti tear ductility ?41N/mm ?40N/mm ?43N/mm
Paper tinsel thickness ?30+8μm ?29+6μm ?31+6μm
Although for the branching agent masterbatch is different carriers, the mechanical property in the inventive embodiments 4 and 5 is closely similar.When using Ecoflex as carrier, thickness distribution is more favourable.Yet difference is very little.High by 50% in the inventive embodiments 6 in the ratio inventive embodiments 4 and 5 of branching agent.This has reduced the fracture tension strain.Because low MVR, bubble stability is in inventive embodiments 4 and 5.
Use the fluidity testing of melt volume-flow rate (MVR) to obtain following result according to ISO 1133:
Inventive embodiments 4:MVR=3.0ml/10min
Inventive embodiments 5:MVR=1.2ml/10min
Inventive embodiments 6:MVR=0.6ml/10min.
Inventive embodiments 4 and 5 has the concentration of identical Joncryl ADR 4368 in the Ecoflex/PLA of compounding material.Surprisingly, inventive embodiments 5 demonstrates significantly lower MVR.Therefore, the branching agent masterbatch based on Ecoflex has more advantage than the branching agent masterbatch based on PLA.
The Ecoflex solid support material that is used for Ecoflex masterbatch FBA branching agent is compared additional advantage with PLA as solid support material and is the higher PLA per-cent of sneaking into, and does not sacrifice Ecoflex phase favourable in the compounding material.In addition, under identical compounding condition, obtain than using PLA as the masterbatch of the solid support material of branching agent as the obviously more low-level spot of the masterbatch of the solid support material of branching agent with Ecoflex.
Embodiment 7 (with the PHB blend)
The compounding material that will comprise following component is 40mm at diameter, turns round in the duplex kneader that is rotated counterclockwise:
●63.7％Ecoflex
Figure G05846474920070716D000191
F?BX?7011(BASF?Aktiengesellschaft)，
● 16.0% poly butyric ester is (from the Biocycle of PHB Industrial S/A PHB 94),
●8.4％PLA(NatureWorks
Figure G05846474920070716D000193
4041?D，Cargill?Dow)，
● 6.0% lime carbonate (Hydrocarb OG),
● 4.2% titanium dioxide (Kronos 2200, Bayer AG),
● 0.4% polyoxyethylene glycol (Pluriol
Figure G05846474920070716D000194
1500, BASF Aktiengesellschaft),
● 0.4% lubricant (Edenol
Figure G05846474920070716D000195
D 82, Cognis),
● 0.4% branching agent is (from the Joncryl of Johnson Polymer
Figure G05846474920070716D000196
, ADR 4368),
[the branching agent ratio of mixture is 10/90 Joncryl/Ecoflex compounding, and uses (4.0 weight %) with the form of pellet in the compounding material]
● 0.5% Zinic stearas (Zincum PS).
Component is predrying, be pre-mixed with dried forms, and introduce by the pellet funnel.Specify following processing parameter:
Melt temperature: about 160 ℃,
Speed of rotation: 150rpm,
Output: 30kg/h.
Is 40mm with the compounding material at screw diameter, and having flute profile intake zone and die diameter is 150mm, and die gap is wide for processing to obtain the blown film that is used for shopping bag that thickness is 60 μ m on the blown film device of 0.8mm.
Here used following processing parameter:
Speed of rotation: 731rpm,
Output: 27kg/h,
Pressure: 135 crust,
Traction: pulling speed 5.4m/min,
Barrel temperature: in forcing machine 150/160/165 ℃,
Temperature: 170/165/165 ℃.
Because the low relatively viscosity of PHB component is although low-level relatively bucket district only can reach appropriate bubble stability.It obviously improves by distinguishing 10 to 15 ℃ of temperature reductions.
Comprise Ecoflex/PHB compounding material, thickness is that the paper tinsel of 60 μ m has following mechanical property:
Test Unit Standard Ecoflex/PHB/PLA
Thickness (on average) μm ? 61
Tension test, parallel MPa ISO?527 502
The alternation tensile strength, parallel MPa ISO?527 27.7
The fracture tension strain, parallel ％ ISO?527 419
? ? ? ?
Tension test, vertical MPa ISO?527 301
The alternation tensile strength, vertical MPa ISO?527 26.8
The fracture tension strain, vertical ％ ISO?527 540
? ? ? ?
Paracentesis resistance N/mm DIN 53373 26.6

Claims (18)

1. biologically-degradable polyester mixture that comprises following component:
I) based on the gross weight of component i-ii, 40-60 weight % is at least a based on aliphatic series and aromatic dicarboxylic acid with based on the polyester of aliphatic dihydroxy compound; With
Ii) based on the gross weight of component i-ii, at least a biodegradable equal polyester of 60-40 weight % or copolyesters, described equal polyester or copolyesters are selected from polylactide, polyhydroxyalkanoatefrom and comprise aliphatic dicarboxylic acid and comprise the polyester of aliphatic diol; With
Iii) based on the gross weight of component i-ii, 0.1-15 weight % comprises the multipolymer of vinylbenzene and glycidyl methacrylate; With
Iv) 0-15 weight % additive; And
The v) inorganic or organic filler of 0-50 weight %,
Wherein component i forms external phase or common external phase.
2. according to the biologically-degradable polyester mixture of claim 1, wherein component i is the polyester based on following component:
A) comprise the acid constituents of following component:
A1) at least a aliphatic series of 30-99 mole % or at least a cycloaliphatic dicarboxylic acid, or its one-tenth ester derivative, or these mixture,
A2) at least a aromatic dicarboxylic acid of 1-70 mole %, or its one-tenth ester derivative, or these mixture, and
A3) 0-5 mole % comprises the compound of sulfonate group,
A1 wherein)-a3) adding up to molar percentage is 100%; With
B) comprise at least a C 2-C 12Alkanediol or a kind of C 5-C 10The diol component of cycloalkanes glycol, or these mixture;
And one or more are selected from the component of following component if necessary:
C) be selected from the component of following component:
C1) at least a dihydroxy compound that comprises ether official energy and have formula I:
HO-[(CH 2) n-O] m-H (I)
Wherein n be 2,3 or 4 and m be the integer of 2-250,
C2) hydroxycarboxylic acid of at least a formula IIa or IIb:
Wherein p is the integer of 1-1500, and r is the integer of 1-4, G for be selected from phenylene ,-(CH 2) q-,-C (R) H-and-C (R) HCH 2Group, wherein q is the integer of 1-5, R is methyl or ethyl,
C3) at least a amino-C 2-C 12Alkanol, or at least a amino-C 5-C 10Cycloalkanol, or these mixture,
C4) at least a diamino-C 1-C 8Alkane,
C5) 2 of at least a formula III, 2 '-two
Figure DEST_PATH_FSB00000502390900022
The azoles quinoline:
Figure DEST_PATH_FSB00000502390900023
R wherein 1Be singly-bound, (CH 2) z-alkylidene group or phenylene, z=2,3 or 4 wherein,
C6) at least aly be selected from naturally occurring amino acid, by dicarboxylic acid with 4-6 carbon atom and the available polymeric amide of diamines polycondensation with 4-10 carbon atom, the aminocarboxylic acid of the compound of formula IVa and IVb:
Figure DEST_PATH_FSB00000502390900024
Wherein s is the integer of 1-1500, and t is the integer of 1-4, T for be selected from phenylene ,-(CH 2) u-,-C (R 2) H-and-C (R 2) HCH 2-group, wherein u is the integer of 1-12, R 2Be methyl or ethyl,
And have the poly-of repeating unit V
Figure DEST_PATH_FSB00000502390900025
The azoles quinoline:
Figure DEST_PATH_FSB00000502390900031
R wherein 3Be hydrogen, C 1-C 6Alkyl, C 5-C 8Cycloalkyl, unsubstituted or have three C at the most 1-C 4The phenyl of alkyl substituent, or tetrahydrofuran base,
Or comprise c1)-c6) mixture;
And
D) be selected from the component of following component:
D1) at least a compounds with at least three one-tenth ester groups,
D2) at least a isocyanic ester and
D3) at least a divinyl ether,
Or comprise d1)-d3) mixture.
3. according to the biologically-degradable polyester mixture of claim 2, wherein at component i) in
Described aliphatic series or cycloaliphatic dicarboxylic acid (component a1)) be succsinic acid, hexanodioic acid or sebacic acid, it becomes ester derivative, or these mixture;
Described aromatic dicarboxylic acid (component a2)) be terephthalic acid or its one-tenth ester derivative, and
Described diol component (B component) is 1,4-butyleneglycol or 1, ammediol.
4. according to each biologically-degradable polyester mixture among the claim 1-3, wherein component ii is: polylactide, poly-beta-hydroxy-butyrate or poly-beta-hydroxy-butyrate-altogether-valerate.
5. according to the biologically-degradable polyester mixture of claim 1, wherein component i forms external phase.
6. according to each biologically-degradable polyester mixture among the claim 1-3, it comprises the gross weight 0.1-10 weight % component iii based on component i-ii.
7. according to the biologically-degradable polyester mixture of claim 4, it comprises the gross weight 0.1-10 weight % component iii based on component i-ii.
8. according to the biologically-degradable polyester mixture of claim 5, it comprises the gross weight 0.1-10 weight % component iii based on component i-ii.
9. method for preparing according to each biologically-degradable polyester mixture among the claim 1-8, it is included in the step blending ingredients i, ii and iii and makes these component reaction.
10. method for preparing according to each biologically-degradable polyester mixture among the claim 1-8, it is included in the first step 5-35 weight % component iii is mixed under 110-145 ℃ to obtain the branching agent masterbatch with 65-95 weight % component i, if and component ii and suitable other component i are mixed with this branching agent masterbatch, and make the mixture that comprises component i, ii and iii that obtains 150-250 ℃ of reaction down.
11. according to the method for preparing biologically-degradable polyester mixture of claim 9, wherein other component ii) adds in extra step (3).
12. according to the method for preparing biologically-degradable polyester mixture of claim 10, wherein other component ii) adds in extra step (3).
13. according to each the method for preparing biologically-degradable polyester mixture among the claim 9-12, wherein in one of step (1)-(3) or institute in steps in adding polymerization or oligomeric sebacic acid-1, ammediol ester and/or polymerization or oligomeric sebacic acid-1, the 4-butanediol ester.
14. branching agent masterbatch that comprises following component:
In 5-35 weight % such as the claim 1 definition component iii and
The component i that 65-95 weight % such as claim 1-3 define in each.
15. according to the branching agent masterbatch of claim 14, it comprises:
10-20 weight % component iii and
80-90 weight % component i.
16. according to each the purposes of biologically-degradable polyester mixture in producing moulded product, paper tinsel or fiber among the claim 1-8.
17. comprise moulded product, paper tinsel or fiber according to each biologically-degradable polyester mixture among the claim 1-8.
18. by moulded product, paper tinsel or the fiber of producing according to the method for claim 11 or 12.
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