CN1281482A - Stabilized molding compounds comprised of biologically degradable materials - Google Patents

Stabilized molding compounds comprised of biologically degradable materials Download PDF

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CN1281482A
CN1281482A CN98811939A CN98811939A CN1281482A CN 1281482 A CN1281482 A CN 1281482A CN 98811939 A CN98811939 A CN 98811939A CN 98811939 A CN98811939 A CN 98811939A CN 1281482 A CN1281482 A CN 1281482A
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acid
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alcohol
ester
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M·福格特
K·杰施克
A·埃克特
V·米勒
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention relates to stabilized thermoplastic molding compounds comprised of biologically degradable polymers which are stabilized against hydrolytic and microbial degradation and a method for producing concentrates based on thermoplastic biologically degradable polymers. The invention also relates to a method for producing hydrolysis stabilized and antimicrobial or microbistatic acting thermoplastic biologically degradable molding compounds as well as to the utilization of the inventive stabilized molding compounds as biologically degradable materials for the production of semi-finished goods, films, injection molded parts, monofilaments, multifilaments, fibers, nonwovens and wovens.

Description

Biodegradable material stabilized molding compounds comprised
The present invention relates to a class is stable to hydrolytic deterioration and microbiological deterioration, the thermoplastic composition of biodegradable polymers, a kind of preparation method of the masterbatch based on the thermoplastic biologically degradable polymkeric substance, the preparation method of the moulding compound of a kind of hydrolysis thermoplastic biologically degradable stable and that have anti-microbial effect or microbiologically stabilised effect, with the application of making following goods as biodegradable material according to the stable moulding compound of the present invention, comprise work in-process, film, injection-molded item, monofilament and multifilament, fiber, the application of supatex fabric and woven fabrics, and by the molded article or the work in-process of its manufacturing, film, injection-molded item, monofilament and multifilament, fiber, supatex fabric and woven fabrics itself.
Known biodegradable plastics (referring to, for example, EP-A 561224, EP-A641817).Same known hydrolysis stabilizer and sterilant and microbiologically stabilised active compound (referring to, for example, 9th corrected and improved edition of R mpp ChemieLexikon on CD-ROM, version 1.0, Thieme Verlag, keyword " Stabilisatoren ", " Mikrobizid ", " Preventol ", " Carbodiimid ").
Many Biodegradable materials generally are subject to the influence of hydrolytic deterioration process, this hydrolytic deterioration process is not only carried out under the moving situation about existing of little life in soil, water and mixed fertilizer, and under the situation that moisture exists, already at the pellet lay up period with during product prepared therefrom is used, slowly to carry out to the moderate speed.
The objective of the invention is control, particularly, slow down this early stage degraded and described material loss of energy, but therefore do not make the desired biological degradation of the component end item after using be lost to attractive degree.
Another purpose is the package stability by work in-process that prepare according to moulding compound of the present invention and component end item to be increased, and prolonged its work-ing life, particularly under humid conditions.Have now found that, additive and stablizer be added in the biodegradable polymkeric substance, can make biological degradation and hydrolytic deterioration begin obtain postponing, so, in long-term purposes, can adopt this class material, for example, at the building section or in landscape is arranged.
The invention provides the moulding compound of thermoplastic biologically degradable, it comprises biodegradable polymkeric substance and at least a group A1 that is selected from) and stablizer A2).
A1) 0～50% wt%, preferred 0.001～30 wt%, preferred especially 0.05～5wt%'s, in the total mixture is benchmark, be selected from the stablizer of at least a following hydrolysis stabilizer, promptly, for example aliphatic series or aromatic monomer, oligomeric or polymerization carbodiimide, as: the carbodiimide of amido-containing acid ester, N, N '-dicyclohexylcarbodiimide, N-glycidyl phthalimide, has isocyanate terminated base, 1 of urea groups and/or carbamate groups, two (1-methyl isophthalic acid-isocyanato--ethyl) benzene of 3-, two (trimethyl silyl)-carbodiimides, Duo Guan Neng oxazoline, multi-functional epoxyization thing and polyfunctional isocyanate; Carbodiimide preferred polymeric or polymer-bound, it can, for example, adopt typical catalyst to make aromatics or aliphatic isocyanate carry out polymerization, and be accompanied by emitting of carbonic acid gas and make, described isocyanic ester is for example: isocyanic acid 2, the 6-6-diisopropyl benzene ester, 1,3,5-triisopropyl-2,4-two isocyanato-benzene, naphthalene 1, the 5-vulcabond, 2,4-two isocyanato-s-3,5-diethyl toluene, 4,4 '-methylene radical-two (isocyanic acid 2,6-diethyl phenyl ester), 4,4 '-methylene radical-two (isocyanic acid 2-ethyl-6-toluene ester), 4,4 '-methylene radical-two (isocyanic acid-2-sec.-propyl-6-toluene ester), 4,4 '-methylene radical-two (isocyanic acid-2,6-6-diisopropyl benzene ester) and 4,4 '-methylene radical-two (isocyanic acid 2-ethyl-6-methyl cyclohexane ester) and
A2) 0～50% wt%, preferred 0.001～30 wt%, preferred especially 0.01～5wt%'s, in the total mixture is benchmark, be selected from the stablizer of at least a following antiseptic-germicide, for example, thiuram, sulfo-phthalimide, sulphonamide, urea derivatives, triazole derivative, triazoline derivative, benzimidizole derivatives, benzimidazolyl-carbamic acid derivative, aryl sulfone, sulfenyl sulfonamides, phenol and phenolate, sulfo-benzothiazole derivant, amino alcohol, isothiazolinone, benzothiazoles and pyrethroid and
B) 0～85 wt% is a benchmark in the total mixture, filler and strongthener, and preferably with natural mineral, synthesizing inorganic or the natural organic matter on recyclable raw-material basis, perhaps synthetic organic and metallics, perhaps several these mixture of ingredients.
Especially preferably by the authorization can with food or the contacted carbodiimide of its mixture.
The present invention also provides with this additive masterbatch as the basis of biodegradable polymkeric substance.Up to the present, can not satisfy the requirement of complete biodegradable based on masterbatch such as polyethylene or polyester etc.Yet,, therefore, be difficult to the known conventional masterbatch is evenly sneaked in the biodegradable polymkeric substance such as based on the conventional masterbatch of aromatic polyester and biodegradable normally aliphatic series or only partly be that the melting range difference of plastics of aromatics is extensive.The advantage that has based on the masterbatch of biodegradable plastics is that the material consistency is good, and is relevant therewith, additive being evenly distributed in particular substrate.Masterbatch comprises 40 wt% stablizers at the most usually, is preferably 1～30 wt%, and particularly 5～20 wt% are benchmark in the total mixture.
Suitable biodegradable polymkeric substance is, for example, aliphatic polyester or copolyesters, aromatic polyester or copolyesters, aromatic-aliphatic copolyesters, polycarbonate, polyester-carbonic ether, aliphatic series or partially aromatic polyester-urethane, polyester-amides, polyether-amide, polyether-ester-amide, ether of cellulose, cellulose ether-esters, thermoplastic starch, starch derivative or multipolymer or these mixture of ingredients.
Following polymkeric substance suits, and is that institute is preferred:
Aliphatic series or partially aromatic polyester, from following formation:
A) aliphatic diol, preferred line style C 2～C 10Glycol, for example: ethylene glycol, butyleneglycol or hexylene glycol, preferred especially butyleneglycol, and/or optional alicyclic dibasic alcohol, preferred alicyclic ring has 5 or 6 carbon atoms, for example, cyclohexanedimethanol, and/or, instead of part or whole glycol, employing is up to 8000, preferably is up to 4000 their multipolymer based on the monomer of ethylene glycol, propylene glycol or tetrahydrofuran (THF) or oligomeric polyvalent alcohol or molecular weight, and/or optional a small amount of side chain dibasic alcohol, preferred C 3～C 12Alkyl diol, for example, neopentyl glycol, the alcohol of also optional a small amount of higher functionality, for example, and 1,2,3-glycerol or TriMethylolPropane(TMP); And, aliphatic dibasic acids, preferred C 2～C 12The alkyl dicarboxylic aid, for example with preferred, succsinic acid or hexanodioic acid, and/or optional aromatic diacid, for example, terephthalic acid, m-phthalic acid or naphthalene dicarboxylic acids and the also acid of optional a small amount of higher functionality, for example, trimellitic acid; Or
B) have the acid and the structural unit of carbinol-functional group, preferably in alkyl chain, contain 2～12 carbon atoms, for example, hydroxybutyric acid, hydroxyl valeric acid or lactic acid perhaps have its derivative person, for example, 6-caprolactone or dilactide, or the mixture of A and B and/or multipolymer; In all acid is benchmark, and aromatic acid content is not more than 50 wt%.
Aliphatic series or partially aromatic polyester-urethane, from following formation:
C) aliphatic diol, preferred line style C 2～C 10Glycol, for example, ethylene glycol, butyleneglycol or hexylene glycol, preferred especially butyleneglycol, and/or optional alicyclic dibasic alcohol preferably have C 5Or C 6-alicyclic ring, for example, cyclohexanedimethanol, and/or instead of part or whole glycol, adopt based on the monomer of ethylene glycol, propylene glycol or tetrahydrofuran (THF) or oligomeric polyvalent alcohol or molecular weight and be up to 4,000, preferably be up to 1,000 their multipolymer, and/or optional a small amount of side chain dibasic alcohol, preferred C 3～C 12Alkyl diol, for example neopentyl glycol and the also alcohol of optional a small amount of higher functionality, preferred C 3-C 12Alkyl polyols, for example, 1,2,3-glycerol or TriMethylolPropane(TMP); And aliphatic dibasic acids, preferred C 2～C 12The alkyl dicarboxylic aid, for example with preferred, succsinic acid or hexanodioic acid, and/or optional aromatic diacid, for example, and terephthalic acid, m-phthalic acid or naphthalene dicarboxylic acids and the also acid of optional a small amount of higher functionality, for example, trimellitic acid; Or
D) have the acid and the structural unit of carbinol-functional group, preferably contain 2～12 carbon atoms, for example, hydroxybutyric acid, hydroxyl valeric acid or lactic acid perhaps have its derivative person, as 6-caprolactone or dilactide, perhaps C) and mixture D) and/or multipolymer,
In all acid is benchmark, and aromatic acid content is not more than 50 wt%;
E) following reaction product, promptly, the isocyanic ester of C and/or D and aliphatic series and/or alicyclic diisocyanate and also optional higher functionality, preferably contain 1～12 carbon atom, perhaps under the situation of alicyclic isocyanate, contain 5～8 carbon atoms, for example, tetramethylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate, the alcohol of also optional and line style and/or side chain and/or alicyclic dibasic alcohol and/or higher functionality, preferred C 3～C 12Alkyl two or polyvalent alcohol, or under the situation of alicyclic alcohol 5～8 carbon atoms, as ethylene glycol, hexylene glycol, butyleneglycol or cyclohexanedimethanol, and/or amine and/or amino alcohol also optional and line style and/or side chain and/or cycloalphatic diamine and/or amino alcohol and/or higher functionality, in alkyl chain, preferably contain 2～12 carbon atoms, for example, quadrol or monoethanolamine, and/or optional in addition modified amine or alcohol, for example, ethylene ethylamine-sulfonic acid is with free acid or with the form of salt
In C), D) and E) sum be benchmark, C) and/or D) ester content is at least 75 wt%.
Aliphatic series or aliphatic-aromatic polyesters-carbonic ether, from following formation:
F) aliphatic diol, preferred line style C 2～C 10Glycol, for example, ethylene glycol, butyleneglycol or hexylene glycol, preferred especially butyleneglycol, and/or optional alicyclic dibasic alcohol preferably contain 5～8 carbon atoms in alicyclic ring, for example, cyclohexanedimethanol, and/or, instead of part or whole glycol, employing is with ethylene glycol, propylene glycol or tetrahydrofuran (THF) are monomer or the oligomeric polyvalent alcohol or the molecular weight maximum 4,000 on basis, preferred maximum 1,000 their multipolymer, and/or optional a small amount of side chain dibasic alcohol, for example, neopentyl glycol and the also alcohol of optional a small amount of higher functionality, for example, 1,2,3-glycerol or TriMethylolPropane(TMP); And aliphatic dibasic acids, preferably use C 2～C 12The alkyl dicarboxylic aid, for example with preferred, succsinic acid or hexanodioic acid, and/or optional aromatic diacid, for example, terephthalic acid, m-phthalic acid or naphthalene dicarboxylic acids and the also acid of optional a small amount of higher functionality are as trimellitic acid; Or
G) have the acid and the structural unit of carbinol-functional group, preferably in alkyl chain, contain 2～12 carbon atoms, for example hydroxybutyric acid, hydroxyl valeric acid or lactic acid, or have its derivative person, as 6-caprolactone or dilactide, or F) and mixture G) and/or multipolymer,
In all acid is benchmark, and the content of aromatic acid is not higher than 50 wt%;
H) by the aromatics dihydric phenol, preferred dihydroxyphenyl propane and carbonic ether are given body, as phosgene, and the carbonic ether content of preparation, perhaps by the aliphatic carbonate or derivatives thereof, and chlorinated carbonates, or the aliphatic carboxylic acid or derivatives thereof, as salt, give body with carbonic ether, as phosgene, preparation and carbonic ether content
In F), G) and H) sum be benchmark, F) and/or G) ester content is at least 70 wt%.
Aliphatic series or partially aromatic polyester-amides or polyethers ester-acid amide, from following formation:
I) aliphatic diol, preferred line style C 2～C 10Glycol, for example, ethylene glycol, butyleneglycol or hexylene glycol, preferred especially butyleneglycol, and/or optional alicyclic dibasic alcohol, preferably it contains 5～8 carbon atoms, for example, cyclohexanedimethanol, and/or, instead of part or whole glycol adopt monomer or oligomeric polyvalent alcohol or molecular weight maximum 10,000, preferred maximum 8 based on ethylene glycol, propylene glycol or tetrahydrofuran (THF), 000, preferred especially maximum 5,000 their multipolymer, and/or optional a small amount of side chain dibasic alcohol, preferred C 3～C 12-alkyl diol, for example, the alcohol of neopentyl glycol and also optional a small amount of higher functionality, preferred C 3～C 12-alkyl polyols, for example, 1,2,3-glycerol or TriMethylolPropane(TMP); And aliphatic dibasic acids, preferably in alkyl chain, contain 2～12 carbon atoms, for example with preferred, succsinic acid or hexanodioic acid, and/or optional aromatic diacid, for example, terephthalic acid, m-phthalic acid or naphthalene dicarboxylic acids, the also acid of optional a small amount of higher functionality, for example, trimellitic acid; Or
K) have the acid and the structural unit of alcohol functional group, preferably in carbochain, contain 2～12 carbon atoms, for example hydroxybutyric acid, hydroxyl valeric acid or lactic acid, or have its derivative person, as 6-caprolactone or dilactide,
Or I) and mixture K) and/or multipolymer, be benchmark in all acid, aromatic acid content is not more than 50 wt%,
L) from following acid amides content, aliphatic series and/or alicyclic binary and/or optional a small amount of side chain diamine, the preferred compound of institute is linear aliphatic C 2～C 10The amine of diamines and also optional a small amount of higher functionality and in amine preferred hexamethylene-diamine or isophorone diamine and preferred especially hexamethylene-diamine; And line style and/or alicyclic diprotic acid, preferably in alkyl chain, contain 2～12 carbon atoms, or be C under the situation of alicyclic acid 5Or C 6-ring, preferred hexanodioic acid, and/or optional a small amount of side chain binary and/or optional aromatic diacid, for example, terephthalic acid, m-phthalic acid or naphthalene dicarboxylic acids and the also acid of optional a small amount of higher functionality preferably contain 2～10 carbon atoms; Or
M) have the acid amides content of the acid and the structural unit of amine functional group, preferably in alicyclic chain, contain 4～20 carbon atoms, preferred omega-lauryl lactan or ε-Ji Neixianan, especially preferred ε-Ji Neixianan,
Or L) and mixture M) as the acid amides content, in I), K), L) and M) and be benchmark, I) and/or K) weight content of ester content at least 30 wt% and preferred ester structure is that 30～70 wt% and amide structure content are 70～30 wt%.
Polyether-ester-amide from, especially, following monomer constitutes:
Oligomeric polyvalent alcohol, comprise polyoxyethylene glycol, polypropylene glycol, random or block form, from the polyoxyethylene glycol of the mixture preparation of oxyethane or propylene oxide, or polytetrahydrofuran, its molecular weight (weight average) be 100～10,000 and
Monomeric diol, preferred C 2～C 12-alkyl diol, particularly C 2-C 6Alkyl diol, ethylene glycol, 1 for example, 4-butyleneglycol, 1, ammediol or 1,6-hexylene glycol and at least aly be selected from following monomer:
Dicarboxylic acid, preferred C 2～C 12-, preferred especially C 2～C 6Alkyl dicarboxylic aid, for example oxalic acid, succsinic acid or hexanodioic acid, the form (methyl, ethyl etc.) of their specific ether in addition
C 2～C 12Alkyl hydroxy carboxylic acid and lactone, especially, caprolactone for example
The amino alcohol that contains 2～12 carbon atoms in alkyl chain is as thanomin or Propanolamine
Contain 5～12, the cyclic lactam of preferred 6～11 carbon atoms, as ε-Ji Neixianan or lauryl lactan etc.
The omega-amino-carboxylic acid that contains 6～12 carbon atoms in alkyl chain is as hexosamine etc.
Such as C such as hexanodioic acid or succsinic acids 2～C 12-alkyl dicarboxylic aid and such as C such as hexamethylene-diamine or diaminobutanes 2～C 12The mixture of alkyl diamine (1: 1 salt).
Having polyester hydroxyl or acid end group, molecular weight 300～10,000 also can be as the composition that forms ester.
The share of ether and ester content is generally 5～85 wt% in polymkeric substance, is benchmark in all polymkeric substance.
Molecular-weight average according to polyether-ester-amide of the present invention is generally 10,000～300, and 000, be preferably 15,000～150,000, preferred especially 15,000～100,000 (, in cresols, being the Mw that standard specimen is measured) with the polystyrene by gel chromatography.
All acid also all can be used with the form of derivative, and for example, acyl chlorides or ester are with monomer with the form of oligomeric ester.
Can be undertaken by " polymeric amide method " and " polyester method " according to the synthetic of biodegradable polyester-acid amides of the present invention; In the polymeric amide method, initial composition is mixed with stoichiometric quantity,, be accompanied by and add entry, from reaction mixture, remove again subsequently and anhydrate if suitable; And in the polyester method, initial composition is mixed with stoichiometric quantity, and add excess diol, be accompanied by the esterification of acid groups and the transesterify or the acid amides of these esters of carrying out subsequently exchange.Under second kind of situation, adding under the condition of entry, excess diol also is distilled out.Preferred employing described " polyester method " is synthesized.
In addition, can adopt known catalyzer that polycondensation is quickened.Quicken the known phosphorus compound of polymeric amide synthetic and be used for the acid of esterification or organo-metallic catalyst and both combinations all can be quickened the reaction of polycondensation.
Should guarantee that catalyzer is to biodegradable or make into the ability (compostability) of compound manure or the quality of compound manure does not all have detrimentally affect.In addition, the influence of the use of the hard to bear following substances of polycondensation energy of preparation polyester-amides, promptly, Methionin, lysine derivative or because of forming other product of acid amides branching, for example, the aminoethyl monoethanolamine, this two class all quicken condensation reaction and cause branched product (referring to, for example, DE-A3831709).
The preparation of polyester, polyester-carbonic ether and polyester-urethane is well-known, perhaps can be undertaken by the similar approach of currently known methods (referring to, for example, EP-A-304,787, WO 95/12629, WO 93/13154, EP-A-682054 and EP-A-593975).
Can also comprise 0.1～5 wt% branching agent according to polyester of the present invention, polyester-urethane, polyester-carbonic ether or polyester-amides, be preferably 0.1～1 wt% (also referring to, about the narration of polymkeric substance).These branching agents can be trivalent alcohols for example, as TriMethylolPropane(TMP) or glycerine; Tetravalent alcohol is as tetramethylolmethane; Perhaps tribasic carboxylic acid is as citric acid.Branching agent makes the melt viscosity according to polyester-amides of the present invention, and being increased to the extrusion blow that makes these polymkeric substance becomes possible degree.As its result, the biological degradability of these materials is not affected.
Biodegradable/as can to become the molecular weight of (compostable) polyester-urethane, polyester, polyester-carbonic ether and the polyester-amides of compound manure to be generally at least 10,000g/mol, initiator are generally random distribution in polymkeric substance.At optional C) and D) and E) in the polyurethane(s) type polymkeric substance made, always do not expect that the monomer structure unit is entirely random distribution.
Particularly preferred poly-carbodiimide is to be the adjacent position with respect to carbodiimide group by the poly-carbodiimide of the aromatics that isopropyl group replaced, promptly on phenyl ring 2, and 6-or 2,4,6-position.The molecular-weight average of poly-carbodiimide of the present invention is preferably 1,500-15, and 000, but especially be preferably 9,000～12,000.Especially, can increase thermo-oxidative stability, so that the endgroup content of bio-degradable plastics is not fallen, obtain to have the biodegradable plastics of stability to hydrolysis like this by adding a small amount of aromatics and/or aliphatic series (gathering) carbodiimide.
Following carbodiimide can be used as example:
Figure 9881193900141
Wherein, P is determined by molecular weight.
Carbodiimide can be by original known method preparation (for example DE-AS 2537685, DE-AS 1156401, DE-AS 2419968 and FR 1180307).
The filler and the strongthener that suit according to the present invention can be mineral, for example, kaolin, chalk, gypsum, mica, lime or talcum, perhaps naturally occurring material, for example, starch or treated starch, Mierocrystalline cellulose or derivatived cellulose or cellulose product, wood powder or natural fiber are as hemp, flax, sisal hemp, rape Huo Limonene fiber crops.The metallic stuffing that can also use is iron powder, ferric oxide, iron alloy (as: ferrotianium, molybdenum-iron, ferromanganese), tungsten, wolfram varbide, ferrotungsten, molybdenum, manganese, cobalt, copper, zinc, tin or bismuth, or its combination.
According to of the present invention biodegradable/can become fully in polyester-urethane, polyester, polyester-carbonic ether and the polyester-amides of compound manure, can add conventional additives.Like this, can use properties-correcting agent and/or processing aid, for example, nucleating agent, softening agent, releasing agent, fire retardant, impact modifiers, for example thermally-stabilised, oxidation-stabilized and UV stable and photostabilizer, tinting material (as, pigment) or other additive that in thermoplastics art, uses, but should guarantee that do not damage and can become compound manure fully, the perhaps remaining material such as mineral assistant is harmless in compound manure.General additive add-on mostly is 15 wt% most, is benchmark in whole mixtures.
According to moulding compound of the present invention is biodegradable, preferably all degradable.According to DIN 54900, can classify as all degradable those moulding compounds, be particularly preferred.
According to of the present invention biodegradable/can become polyester-urethane, polyester, polyester-carbonic ether and the polyester-amides of compound manure also to mix fully with other blend composition, thermoplastic starch for example, but should guarantee, do not damage and can become compound manure fully, the perhaps remaining material such as the mineral substance auxiliary agent is harmless in compound manure.
Other blend composition that not necessarily can use in other Application Areas at biodegradable is:
Polyethylene, modified poly ethylene, for example use maleic anhydride modified LDPE, the fluorine thermoplastics, for example, tetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/perfluoro alkoxy vinyl ethers multipolymer, Tefzel, polychlorotrifluoroethylene, ethene/chlorotrifluoroethylcopolymer copolymer, poly(vinylidene fluoride), fluorinated ethylene propylene, poly-Fluoroalkyloxy paraffinic hydrocarbons, tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride copolymer, amorphous perfluorinated polymers, polyvinyl chloride, polyvinylidene dichloride, polypropylene, polyvinyl alcohol, Vinyl Acetate Copolymer, the Vinyl Acetate Copolymer of partial hydrolysis, polyvinyl ether, polyethers, polyacrylic ester, aliphatic polyester or copolyesters, aromatic polyester or copolyesters, the aromatic-aliphatic copolyesters, polycarbonate, polyester-carbonic ether, partially aromatic urethane, aliphatic urethane, polyester-urethane, polymeric amide, polyester-amides, polyether-amide, polyether-ester-amide, ether of cellulose, cellulose ether-esters, starch derivative or multipolymer, or the mixture of several mentioned components.
The content of the blend composition that can use is up to 99 wt%, preferably is up to 70 wt%, is benchmark in the moulding compound total amount.
The present invention also provides the method for a kind of preparation according to moulding compound of the present invention, it is characterized in that: each component and optional other additive (conventional additives) are mixed by currently known methods, make mixture be mixed and melt extrude through fusion, at high temperature, preferred 150～300 ℃, equipment used is a conventional equipment, as inner (internal) kneader, forcing machine and twin screw extruder.
The present invention also provides the method for a kind of preparation according to the moulding compound of claim 1～15, wherein, biodegradable polymkeric substance and biodegradable polymer master batch, at least a stablizer A1) or A2) and optional components B) and additive mix, the gained mixture is mixed and melt extrudes through fusion at high temperature.
Employed forcing machine is, for example,
Screw rod meshes fully closely combines twin screw extruder, with the high single screw extrusion machine of the extrusion performance of stator-rotor operate (as: the Staromix  of ReifenHauser), three-screw extruder, continuously/periodical operation CO kneader and disperse kneader continuously, it (for example has slow rotary rotor-stator combination, KEX, Drais, Mannheim).
The present invention also provides the application according to moulding compound of the present invention, be used to prepare work in-process, film, especially hygienic articles film, refuse bag, roof base web layer and garment accessories with film, injection-molded item, especially establish slack tank, equipment clamping plate and equipment tackiness agent, multifilament, monofilament, fiber, staple fibre and fiber in particular for applying heat sealable filter paper, non-woven and woven cloth, especially geotextile, protective clothing and automobile liner and their various goods.
Example
Example 1
With polyester-amides (as, BAK  1095, Bayer company produces) and the poly-carbodiimide of aromatics (as, Stabaxol  P100, Rhein Chemie Rheinau company produces) fusion together under 170～190 ℃ in following twin screw extruder, described forcing machine is that Werner﹠Pfleiderer company (Stuttgart) produces, the ZSK type, L/D has special kneading member than greater than 35, and at least the first intake zone has been cooled.The wire rod of in this way extruding cools off in water-bath, and granulation and drying.
BAK  1095 is hexanodioic acid, butyleneglycol and hexanolactam polyester-amides through random copolycondensation, and wherein ester/acid amides weight ratio is 70/30, and its relative solution viscosity is 2.78, measures under 20 ℃ with 1 wt% m-cresol solution.
BAK  2195 is 32.3 wt% hexanodioic acids, 11.7 wt%1, the polyester-amides that 4-butyleneglycol, 15.0wt% Diethylene Glycol, 41 wt%AH salt are made through random copolycondensation, its relative solution viscosity is 2.8, measures under 20 ℃ with 1 wt% m-cresol solution.
Table 1
The masterbatch (each numeral of composition is wt%) that contains hydrolysis stabilizer
Masterbatch ??A ???B ???C ???D ???E
?BAK1095 ??90 ???90
?BAK2195 ??90 ???90 ???90
?StabaxolP ??10 ??10
?StabaxolP100 ???10 ???10
?StabaxolP200 ???10
Relative solution viscosity ?2.78 ??2.72 ??3.91 ??3.27 ??2.66
Example 2
With BAK  2195 to be injected into strip (80 * 10 * 4 mm) with form by the mixture of the masterbatch of example 1 preparation.Strip is stored in 60 ℃ of water, and Xiang Shuizhong has added the 0.02wt% sodiumazide, its as biocides to reach sterilisation purpose.Gained the results are shown in table 2.
Table 2: the result who in 60 ℃ of water, stores
Period of storage, day Unstable BAK 2195+10 % is from the masterbatch B (being equivalent to 1%Stabaxol P) of example 1 BAK 2195+10 % is from the masterbatch D (being equivalent to 1%Stabaxol P100) of example 1 BAK 2195+10 % is from the masterbatch (being equivalent to 1 %Stabaxol P200) of example 1
????0 ??2.76 ?????2.67 ?????2.75 ?????2.76
????24 ??2.76 ?????2.54 ?????2.66 ?????2.82
????48 ??2.33 ?????2.47 ?????2.49 ?????2.85
????70 ?????2.42 ?????2.48
????72 ?????2.71
????144 ??2.15
????168 ??2.15 ?????2.32 ?????2.40 ?????2.47
????336 ?????2.06 ?????2.08 ?????2.13
????504 ??1.71 ?????1.80???
????648 ??1.59
????672 ?????1.63
????816 ?????1.59 ?????1.61
????840 ?????1.47

Claims (19)

1. thermoplastic composition comprises biodegradable polymkeric substance and at least a group A1 that is selected from) and stablizer A2):
A1) 0～50 wt% is selected from the stablizer of at least a hydrolysis stabilizer, is benchmark in the total mixture,
And/or
A2) 0～50 wt% is selected from the stablizer of at least a antiseptic-germicide, is benchmark in the total mixture; With
B) 0～85 wt% filler and strongthener is benchmark in the total mixture.
2. according to the moulding compound of claim 1, comprise the biodegradable polymkeric substance that is selected from least a following material: aliphatic series (being total to) polyester, aromatic-aliphatic (being total to) polyester, polycarbonate, polyester-carbonic ether, aliphatic series or partially aromatic polyester-urethane, polyester monoamide, polyether-amide, polyether-ester-amide, ether of cellulose, cellulose ether-esters, thermoplastic starch and starch derivative or multipolymer and/or its mixture.
3. according to the moulding compound of claim 1 and 2, wherein polymkeric substance is selected from following polymkeric substance:
Aliphatic series or partially aromatic polyester, it is made of following:
A) aliphatic diol, and/or optional alicyclic dibasic alcohol, and/or instead of part or whole glycol, employing is up to 8 based on the monomer of ethylene glycol, propylene glycol or tetrahydrofuran (THF) or oligomeric polyvalent alcohol or molecular weight, 000 their multipolymer, and/or the optional a small amount of side chain dibasic alcohol and the alcohol of optional a small amount of higher functionality also; And aliphatic dibasic acids, and/or optional aromatic diacid and the also acid of optional a small amount of higher functionality; Or
B) have the structural unit of acid and carbinol-functional group, or have its derivative person, or the mixture of A and B and/or multipolymer,
In all acid is benchmark, and aromatic acid content is not more than 50 wt%;
Aliphatic series or partially aromatic polyester-urethane, it is made of following:
C) aliphatic diol, and/or optional alicyclic dibasic alcohol, and/or instead of part or whole glycol, employing is up to 4 based on the monomer of ethylene glycol, propylene glycol or tetrahydrofuran (THF) or oligomeric polyvalent alcohol or molecular weight, 000 their multipolymer, and/or the optional a small amount of side chain dibasic alcohol and the alcohol of optional a small amount of higher functionality also; And aliphatic dibasic acids, and/or optional aromatic diacid and the also acid of optional a small amount of higher functionality; Or
D) have the structural unit of acid and carbinol-functional group, or have its derivative person, or the mixture of C and D and/or multipolymer,
In all acid is benchmark, and aromatic acid content is not more than 50 wt%;
C) and/or D) and following E) reaction product
E) aliphatic series and/or alicyclic diisocyanate and the also isocyanic ester of optional higher functionality, the alcohol of also optional and line style and/or side chain and/or alicyclic dibasic alcohol and/or higher functionality, and/or also optional and the amine of line style and/or side chain and/or cycloalphatic diamine and/or amino alcohol and/or higher functionality and/or the amine or the alcohol of amido alcohol and/or also optional modification.
In C), D) and E) sum be benchmark, C) and/or D) ester content is at least 75 wt%;
Aliphatic series or aliphatic-aromatic polyesters-carbonic ether, it is made of following:
F) aliphatic diol, and/or optional alicyclic dibasic alcohol, and/or instead of part or whole glycol, employing is up to 4 based on the monomer of ethylene glycol, propylene glycol or tetrahydrofuran (THF) or oligomeric polyvalent alcohol or molecular weight, 000 their multipolymer, and/or the optional a small amount of side chain dibasic alcohol and the alcohol of optional a small amount of higher functionality also; And aliphatic dibasic acids, and/or optional aromatic diacid and the also acid of optional a small amount of higher functionality; Or
G) have the structural unit of acid and carbinol-functional group, or have its derivative person, or the mixture of F and G and/or multipolymer,
In all acid is benchmark, and aromatic acid content is not more than 50 wt%;
With
H) the carbonic ether content that is equipped with to system by aromatics dihydric phenol and carbonic ether, or the carbonic ether content that is equipped with to system by aliphatic carbonate or derivatives thereof and carbonic ether
By F), G) and H) sum be benchmark, F) and/or G) ester content is at least 70 wt%;
Aliphatic series or partially aromatic polyester-amides or polyether-ester-amide, it is made of following:
I) aliphatic diol, and/or optional alicyclic dibasic alcohol, and/or instead of part or whole glycol, employing is up to 10 based on the monomer of ethylene glycol, propylene glycol or tetrahydrofuran (THF) or oligomeric polyvalent alcohol or molecular weight, 000 their multipolymer, and/or the optional a small amount of side chain dibasic alcohol and the alcohol of optional a small amount of higher functionality also; And aliphatic dibasic acids, and/or optional aromatic diacid and the also acid of optional a small amount of higher functionality; Or
K) have the structural unit of acid and carbinol-functional group, or have its derivative person, or the mixture of I and K and/or multipolymer,
In all acid is benchmark, and aromatic acid content is not more than 50 wt%;
With
L) from following acid amides content, aliphatic series and/or alicyclic binary and/or optional a small amount of side chain diamine, also choose the amine of a small amount of higher functionality wantonly, and line style and/or alicyclic diprotic acid, and/or optional a small amount of side chain binary and/or optional aromatic diacid and the also acid of optional a small amount of higher functionality; Perhaps
M) have the acid amides content of the acid and the structural unit of amine functional group,
Or L) and mixture M) as the acid amides content, in I), K), L) and M) sum be benchmark, I) and/or K) the ester content is at least 30 wt%.
4. according to the moulding compound of claim 3, comprise polyether-ester-amide, the latter is made of following monomer:
Oligomeric polyvalent alcohol, comprise polyoxyethylene glycol, polypropylene glycol, random or block form, from the polyoxyethylene glycol of the mixture preparation of oxyethane or propylene oxide, or polytetrahydrofuran, its molecular weight (weight average) is 100-10,000 and
Monomeric diol,
Be selected from following monomer with at least a:
C 2～C 12-alkyl-dicarboxylic acid also has the form of their specific ester,
Diprotic acid and the also optional higher acid of a small amount of functionality, or
Have the acid amides content of the structural unit of acid and amide functional group, in alicyclic chain, contain 4～20 carbon atoms,
Perhaps L) and mixture M) make the acid amides content, in I), K), L) and M) sum be benchmark, I) and/or K) the ester content be at least 30 wt%.
5. according to the moulding compound of claim 1～3, wherein polyester-amides is made of following:
I) aliphatic diol, and/or optional alicyclic dibasic alcohol, and/or instead of part or whole glycol, employing is up to 10 based on the monomer of ethylene glycol, propylene glycol or tetrahydrofuran (THF) or oligomeric polyvalent alcohol or molecular weight, 000 their multipolymer, and/or the optional a small amount of side chain dibasic alcohol and the alcohol of optional a small amount of higher functionality also; And aliphatic dibasic acids, and/or optional aromatic diacid and the also acid of optional a small amount of higher functionality; Or
K) have the structural unit of acid and carbinol-functional group, or have its derivative person, or the mixture of I and K and/or multipolymer,
In all acid is benchmark, and aromatic acid content is not more than 50 wt%;
With
L) from following acid amides content, aliphatic series and/or alicyclic binary and/or optional a small amount of side chain diamine, also choose the amine of a small amount of higher functionality wantonly, and line style and/or alicyclic diprotic acid, and/or optional a small amount of side chain binary and/or optional aromatic diacid and the also acid of optional a small amount of higher functionality; Perhaps
M) have the acid amides content of the acid and the structural unit of amine functional group,
Or L) and mixture M) as the acid amides content, in I), K), L) and M) sum be benchmark, I) and/or K) the ester content is at least 30 wt%.
6. the moulding compound that one of requires according to aforesaid right comprises 0.001～30 wt% according to A1) stablizer, be benchmark in the total mixture.
7. according to the moulding compound of one of aforesaid right requirement, comprise 0.005～5 wt%A1).
8. according to the moulding compound of one of aforesaid right requirement, comprise 0.001～30 wt%A2).
9. according to the moulding compound of one of aforesaid right requirement, comprise 0.01～5 wt%A2).
10. the moulding compound that one of requires according to aforesaid right, wherein component A) be selected from one or more stablizers, the latter is selected from monomer, oligomeric or polymeric carbodiimide, Duo Guan Neng oxazoline, multi-functional epoxyization thing and polyfunctional isocyanate.
11. moulding compound according to claim 10, wherein carbodiimide is selected from carbodiimide, the N of amido-containing acid ester, N '-dicyclohexylcarbodiimide, N-glycidyl phthalimide, have 1 of isocyanate terminated base, urea groups and/or carbamate groups, the carbodiimide of two (1-methyl isophthalic acid-isocyanato--ethyl) benzene of 3-, two (trimethyl silyl)-carbodiimide, polymeric and/or polymer-bound, the latter can make through aromatics or aliphatic isocyanate polymerization, and polymerization is accompanied by division and emits carbonic acid gas.
12. moulding compound according to claim 11, wherein isocyanic ester is selected from isocyanic acid 2, the 6-6-diisopropyl benzene ester, 1,3,5-triisopropyl-2,4-two isocyanato-benzene, naphthalene 1, the 5-vulcabond, 2,4-two isocyanato-s-3,5-diethyl toluene, 4,4 '-methylene radical-two (isocyanic acid 2,6-diethyl phenyl ester), 4,4 '-methylene radical-two (isocyanic acid 2-ethyl-6-toluene ester), 4,4 '-methylene radical-two (isocyanic acid-2-sec.-propyl-6-toluene ester), 4,4 '-methylene radical-two (isocyanic acid-2, the 6-6-diisopropyl benzene ester) and 4,4 '-methylene radical-two (isocyanic acid 2-ethyl-6-methyl cyclohexane ester).
13. moulding compound according to one of aforesaid right requirement, the mixture that comprises a kind of antiseptic-germicide or antiseptic-germicide, antiseptic-germicide are selected from following structured sort: thiuram, sulfo-phthalimide, sulphonamide, urea derivatives, triazole derivative, triazoline derivative, benzimidizole derivatives, benzimidazolyl-carbamic acid derivative, aryl sulfone, sulfenyl sulfonamides, phenol and phenolate, sulfo-benzothiazole derivant, amino alcohol, isothiazolinone, benzothiazoles and pyrethroid.
14. the moulding compound that one of requires according to aforesaid right, wherein, composition B) is selected from naturally occurring mineral, synthesizing inorganic or naturally occurring organic and metallic stuffing and strongthener or its mixture.
15. according to the moulding compound that aforesaid right one of requires, comprise and be selected from least a following additive: properties-correcting agent, processing aid, softening agent, releasing agent, fire retardant, impact modifiers, stablizer and tinting material.
16. according to the preparation method of the moulding compound of claim 1～15, wherein, each component and optional other additive are mixed, make the gained mixture be mixed and melt extrude through high-temperature fusion.
17. preparation method according to the moulding compound of claim 1～15, wherein, biodegradable polymkeric substance and biodegradable polymers masterbatch and at least a stablizer A1) or A2) and optional components B) and additive mix, the gained mixture is mixed and melt extrudes through high-temperature fusion.
18. the application according to the moulding compound of claim 1～15 is used to make work in-process goods, film, roof substrate web, the film as garment accessories, injection-molded item, multifilament, monofilament, fiber, woven fabric and automobile liner.
19. the work in-process goods that make from moulding compound, film, roof substrate web, film, injection-molded item, multifilament, monofilament, fiber, woven fabric and automobile liner as garment accessories according to claim 1-15.
CN98811939A 1997-12-09 1998-11-28 Stabilized molding compounds comprised of biologically degradable materials Pending CN1281482A (en)

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Publication number Priority date Publication date Assignee Title
US6566419B2 (en) 1999-02-25 2003-05-20 Seefar Technologies, Inc. Degradable plastics possessing a microbe-inhibiting quality
JP2001335626A (en) * 2000-05-26 2001-12-04 Toray Ind Inc Aliphatic polyester resin and molding
JP3984440B2 (en) * 2001-06-20 2007-10-03 三菱樹脂株式会社 Resin composition, film and disposal method
JP4120776B2 (en) 2001-07-09 2008-07-16 ソニー株式会社 Biodegradable plastic material, biodegradable plastic molding, and method for producing the biodegradable plastic molding
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JP2005082642A (en) 2003-09-05 2005-03-31 Nisshinbo Ind Inc Hydrolysis resistance stabilizer for ester group-bearing resin and thermoplastic resin composition
JP2006143932A (en) * 2004-11-22 2006-06-08 Mitsubishi Chemicals Corp Aliphatic or alicyclic polyester resin composition
US7468153B2 (en) 2004-12-30 2008-12-23 The Goodyear Tire & Rubber Co. Degradable blading for tire curing molds
ES2337487T3 (en) 2005-09-21 2010-04-26 Raschig Gmbh FORMULATIONS THAT INCLUDE STABILIZING AGENTS AGAINST HYDROLYSIS.
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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4772649A (en) * 1986-12-18 1988-09-20 The Dow Chemical Company Polyesteramide and sufficient carbodiimide to impart improved compression set
DE4018184A1 (en) * 1990-06-07 1991-12-12 Bayer Ag METHOD FOR STABILIZING PLASTICS CONTAINING ESTER GROUPS
DE4126359A1 (en) * 1991-08-09 1993-02-11 Basf Ag OLIGOMER CARBODIIMIDES
JP3337280B2 (en) * 1993-09-14 2002-10-21 株式会社クラレ Polyurethane composition
JP3422642B2 (en) * 1996-12-24 2003-06-30 日清紡績株式会社 Agent and method for improving resistance of ester-containing resin to degradation by microorganisms
US5973024A (en) * 1997-07-09 1999-10-26 Nisshinbo Industries, Inc. Method for control of biodegradation rate of biodegradable plastic

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