CN1976970A - Anaerobically biodegradable polyesters - Google Patents
Anaerobically biodegradable polyesters Download PDFInfo
- Publication number
- CN1976970A CN1976970A CN 200580008900 CN200580008900A CN1976970A CN 1976970 A CN1976970 A CN 1976970A CN 200580008900 CN200580008900 CN 200580008900 CN 200580008900 A CN200580008900 A CN 200580008900A CN 1976970 A CN1976970 A CN 1976970A
- Authority
- CN
- China
- Prior art keywords
- acid
- polyester
- residue
- moles
- molar percentages
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Anaerobically biodegradable polyesters, and compositions and articles of manufacture containing the polyesters are described. Polyesters previously thought to be non-biodegradable under anaerobic conditions have been surprisingly and unexpectedly rendered anaerobically biodegradable by controlling the aromatic monomer content in the polyester. These polyesters can be made into fibers, films, non-woven fabrics, and adhesives. They are suitable for use in absorbent articles such as flushable personal hygiene products.
Description
Technical field
Relate generally to anaerobically biodegradable polyester of the present invention.The invention still further relates to and contain this polyester or by the composition and the article of manufacture of this polyester manufacture.The goods that are particularly useful comprise film, fiber, supatex fabric and tackiness agent.These goods can be used for preparing the end-use goods of other anaerobically biodegradable, for example diaper, feminine hygiene and incontinence panty girdle (incontinencebrief).
Background technology
Film, fiber, moltenly blow screen cloth and other melt spun fibre goods are prepared by thermoplastic polymer, for example polypropylene and polyester.These films, fiber and fibre product are generally used for supatex fabric and contain the composite structure of continuous film; and, for example Wiping article, women and personal hygiene prod, baby diaper, adult-incontinence panty girdle, hospital/operation and other medical disposable product, textile protection and stratiform thing, geotextile (geotextile) and filtration medium of personal care product especially.
Regrettably, the personal care product by conventional thermoplastic polymer preparation is difficult to dispose and place usually refuse landfill or compost facility.A kind of alternative method of disposal likely is to make these products or its component " can break up (flushable) ", and is promptly compatible with the Waste Water Treatment of for example water drain, septic tank etc.Produce another motivation that really can break up goods and be that a lot of above article through after using, are polluted by for example blood or excremental people's body fluid, described body fluid may carry communicable disease.Thereby, provide effective, the low-cost approach of disposing these goods to breaking up of carrying out of these contaminated goods in the mode that limits casual exposure chance.
Traditionally, breaking up property concentrates on the consistency with family and municipal pipeline annex always, and be defined as the small product size that minimizing disposed by the human consumer in aqueous environment ability (for example, but in toilet or industrial hot-water cure in case with dispersive ability after water contacts).Now existing a lot of inventions relate to the consistency that obtains this degree.In U.S. Pat 6,548,592; 6,552,162; 5,281,306; 5,292,581; 5,935,880; With 5,509,913, U.S. Patent application 09/775,312 and 09/752,017, and a lot of methods that solve these demands have been described among the PCT international publication WO01/66666A2.Basically, this consistency depends on physical decomposition guaranteeing to enter the waste water dis posal system, but and unresolvedly carries out occurring in the system of acceptable operating problem on these components/materials depending on the microorganism digestion usually.
Along with the increase as the consuming product volume that can break up the goods introducing, the consistency focus has been transferred to product in case by the influence that disperses the back to wastewater collection and system for handling.Most of systems present low-oxygen environment, from the part anaerobism to complete anaerobism.The ability that goods are degraded under these conditions is the height ideal.
U.S. Patent Application Publication US2002/0042599 has described the trial that the goods with degradation capability under anaerobic are provided.This announcement has reported that polyesteramide, poly-hydroxyl alcohol ester (polyhydroxyalkoate) and composition thereof are that anaerobism is degradable.In comparative example 4a and 4b, this announcement points out that aliphatic polyester Bionolle 3001 and aliphatic-aromatic copolyesters Eastar14766 " do not provide satisfied degradability in anaerobic sludge.”
Therefore, still needing can be at biodegradable polymkeric substance, especially aliphatic-aromatic copolyesters under the anaerobic condition partially or completely, and goods prepared therefrom.
Brief summary of the invention
In one aspect, the present invention relates to aliphatic-aromatic polyesters, the amount of the aromatic monomer that it comprises effectively makes this polyester anaerobism generation biological degradation.In one embodiment, this anaerobically biodegradable polyester comprises: (a) diacid residues comprises the non-aromatics dicarboxylic acid residue of aromatic dicarboxylic acid residue He about 61 molar percentages of about 57-of about 43 molar percentages of about 39-; (b) diol residue comprises 1 of about 100 molar percentages of about 85-, another diol residue of 4-butyleneglycol and about 15 molar percentages of about 0-.In another embodiment, this polyester comprises: (a) diacid residues comprises the terephthalic acid residue of about 43 molar percentages of about 39-and the hexanodioic acid or the pentanedioic acid residue of about 61 molar percentages of Yue 57-; (b) diol residue comprises 1 of about 100 molar percentages, 4-butyleneglycol residue.
On the other hand, the present invention relates to composition, it comprises anaerobically biodegradable polyester and thermoplastic starch, inorganic salt or the two.
Aspect another, the present invention relates to article of manufacture, it is by anaerobically biodegradable polyester of the present invention and preparation of compositions or contain anaerobically biodegradable polyester of the present invention and composition.This goods comprise film, fiber, supatex fabric and tackiness agent.This polyester and composition are particularly useful for absorbing products and tampon applicator assembly.
Detailed Description Of The Invention
Known aliphatic-aromatic polyesters under anaerobic is biodegradable.But when these being exposed to of material excrement systems or down during the common anaerobic condition of aqueous systems, they usually can't be in significantly degraded in rational time.Referring to for example US2002/0042599A1 the 0003rd paragraph and 0091 paragraph.Yet the contriver finds in surprise and unexpectedly, by the amount of aromatic monomer in the restriction polyester, aliphatic-aromatic polyesters can be made anaerobically biodegradable.
Indefinite article used herein " one " expression one or many.
Unless point out separately, otherwise in specification sheets and claims, be used for representing that all numerical value of the amount, character (for example molecular weight), reaction conditions etc. of each composition are interpreted as all modifying with term " about " in all cases.Therefore, unless be illustrated as opposite situation, otherwise be approximation in the digital parameters described in the following description book and the appended claims, it can be attempted the desired properties that obtains and become according to the present invention.With regard to bottom line, each numerical parameter should and be used conventional rounding-off method and understand at least according to giving significant figure.In addition, the scope of mentioning in present disclosure and the claim is intended to clearly comprise entire area but not only is frontier point.For example, the scope of the 0-10 that mentions is intended to disclose all marks between all integers between 0 and 10 (as 1,2,3,4 etc.), 0 and 10 (as 1.5,2.3,4.57,6.1113 etc.) and frontier point 0 and 10.
Although it is proximate expressing numerical range of the present invention and parameter, the numerical value that provides in specific embodiment is reported as far as possible exactly.Yet any numerical value contains certain error that standard deviation certainly led to of finding from their experimental measurements separately inherently.
Be intended to comprise " copolyesters " at term used herein " polyester ".Usually, polyester is meant by the prepared synthetic polymer of the polycondensation of one or more dual functional carboxylic acids and one or more dual functional oxy-compound.Typically, this dual functional carboxylic acid is a dicarboxylic acid, and this dual functional oxy-compound is a dihydroxy alcohol, for example dibasic alcohol and glycol.Polyester can be randomly by one or more hydroxycarboxylic acids (or their derivative that forms polyester) modification.Alternatively, polyester can form by the ring-opening reaction of annular lactone; For example, as poly(lactic acid) for preparing by its ring-type lactide or the polycaprolactone that forms by caprolactone.
Term used herein " aliphatic-aromatic polyesters " refers to contain the polyester from the residue mixture of aliphatic series or alicyclic dicarboxylic acid or two pure and mild aromatic dicarboxylic acids or glycol.
Term " aromatics " refers to that dicarboxylic acid or glycol contain aromatic kernel on main chain, terephthalic acid or 2 for example, 6-naphthalene diacid.
The term " non-aromatics " that this paper uses about dicarboxylic acid, two pure and mild hydroxycarboxylic acid monomers refers to that monomeric carboxyl or oh group do not connect by virtue nuclear.For example hexanodioic acid promptly connects at its main chain not conform on the carbon atom chain of hydroxy-acid group virtue nuclear, and therefore, it is " a non-aromatics "." non-aromatics " is intended to comprise aliphatic series and contains straight or branched as main chain or form aliphatic series and the alicyclic structure that carbon atom is arranged in the form of a ring, for example glycol, diacid and hydroxycarboxylic acid, to form carbon atom can be saturated or paraffinic hydrocarbons attribute, unsaturated (promptly containing non-aromatics carbon-to-carbon double bond), perhaps acetylene series (promptly containing carbon-to-carbon three key).Therefore in the context of specification sheets of the present invention and claim, " non-aromatics " is intended to comprise linear and chain structure (this paper is called " aliphatic series ") and ring texture (this paper is called " alicyclic " or " cyclic aliphatic ") branching.Yet any aromatic substituent that can be connected in aliphatic series or cycloaliphatic diol or diacid or hydroxycarboxylic acid main chain do not planned to get rid of in term " non-aromatics ".In the present invention, described bifunctional carboxylic acid can be a for example hexanodioic acid or aromatic dicarboxylic acid terephthalic acid for example of aliphatic series or cycloaliphatic dicarboxylic acid.Described difunctionality oxy-compound can be for example 1,4 cyclohexane dimethanol of cycloaliphatic diol, the alicyclic diol of linear or branching for example 1,4-butyleneglycol, perhaps aromatic diol quinhydrones for example.
Term used herein " residue " refers to be incorporated into any organic structure in the polymkeric substance by relating to corresponding monomeric polycondensation.
Term used herein " repeating unit " refers to have by the dicarboxylic acid residue of carbonyl oxygen base connection and any organic structure of diol residue or hydroxycarboxylic acid residue.Therefore, dicarboxylic acid residue can be derived from dicarboxylic acid monomer or its relevant acyl halide, ester, salt, acid anhydrides or its mixture.
Term used herein " dicarboxylic acid " is intended to comprise that the polycondensation method that is applicable to glycol produces the dicarboxylic acid of high molecular weight polyesters and any derivative of dicarboxylic acid, comprises its relevant acyl halide, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture.
The optional employed term of modification polyester of the present invention " hydroxycarboxylic acid " refers to monohydroxy-monocarboxylic acid in the context; comprise and be applicable to that polycondensation method or ring-opening reaction produce aliphatic series and cyclic aliphatic hydroxycarboxylic acid and any derivative thereof of high molecular weight polyesters, comprise relevant acyl halide, ester, cyclic ester (comprising for example dimer of lactic acid lactide), salt, acid anhydrides, mixed acid anhydride or its mixture.
Term " anaerobically biodegradable " refers to this polyester, composition or goods (for example film, fiber, supatex fabric, laminate, moulded products etc.) in anaerobism or little aerobic environment (for example in municipal wastewater treatment plant or change the environment that meets with in the activated sewage mud of excrement system), for example 1-3 month can degrade to small part within reasonable time, weaken, break in flakes, decompose or dissolving.
In International Standards Organization, ASTM for example, US Composting Council, GEN (Europe), DIN (Germany) and Asia are being argued material always and whether are being carried out biological degradation completely.Yet, make a general survey of the whole world, although what reach an agreement is that to break and decompose be the early stage step of overall craft, itself and the biodegradable ample evidence of non-general.No matter biological degradation completely is under the condition of aerobic or anaerobism (or falling between), and carbon biological degradation that all can generating material becomes microbial cell material and the final carbonic acid gas that forms.And, although may hint biological degradation, have only final formation carbonic acid gas to be only the indication of complete biodegradable in universally recognized aerobic and the anaerobic biodegradation in the minimizing of tensile strength, elongation, molecular weight, oxygen-consumption or quality.Usually this carbon is completed into CO
2, microbial cell material and inorganic chemistry material be defined as mineralization.
Microorganism shows the tolerance and different demands for the wide region of oxygen.But even the microorganism that is regarded as strictly anaerobic bacterium also metabolism oxygen when oxygen exists, although it grows not well in the presence of this gas.In biodegradable microflora, observed whole aerobic scope.
Saying that strictly term " anaerobism " refers to not have air (or more specifically, no free oxygen), is not aeriferous fully but almost there is not what liquid bio degraded medium.Therefore, the better description for septic tank or sewage environment is little aerobic (air of minute quantity).The novel material adding septic tank or the sewage system (by flushing the toilet) that will have liquid also will inevitably be carried some dissolved oxygens just.Therefore, term used herein " anaerobism " is not its literal meaning.It more is widely used for referring to partially or completely exhaust free oxygen, for example little aerobic environment that meets with usually in septic tank or sewage system.
Reported fully that some compounds only carry out metabolism when not existing oxygen and obtainable oxygen to be exhausted by aerobic and little aerobic bioreactor.Example is phenolic compound and highly chlorinated molecule.The component of aliphatic-aromatic polyesters such as EASTAR BIO copolyesters be not among these compounds.In complete anaerobic environment, observed EASTAR BIO copolyesters and biological degradation can not occur or even break.Really, the EASTAR BIO copolyester film of placing in the broken grass (grass clippings) (having proved it is to have active microbial environment under the aerobic conditions to EASTARBIO) is in anaerobic environment fully after 5 years even do not begin as yet to break.
Also observe in test before, containing percentage ratio, to surpass the biological degradation of film in aerobic environment of terephthalic acid of 48 moles of % very slow, and in little aerobic (part anaerobism) environment even in 6 months, do not begin as yet to break.The biodegradation rate of EASTAR BIO copolyesters in aerobic environment is subjected to the remarkably influenced of terephthalic acid percentage ratio.The film that but the percentage ratio of the identical terephthalic acid of thickness is low in aerobic environment (for example 41-43 mole %) than the film that contains 46-48 mole % terephthalic acid with the index scale speed biological degradation, and go up several magnitude soon than the film that contains 50 moles of terephthalic acids more than the %.The initial period of also having reported anaerobic biodegradation has " extremely Chang environmental adaptation cycle ".Research before, and especially the film of 48% terephthalic acid can not break under the anaerobic condition fully, this makes most researchers think that aliphatic-aromatic polyesters is not the material standed for of being used to excrement environment/sewage environment.
Yet, in this feasibility study of quoting under very low terephthalic acid percentage ratio (for example being lower than 43 moles of %), aliphatic-aromatic polyesters can break and mineralising changing under excrement/sewage condition really.
Usually by dicarboxylic acid and glycol preparation, it reacts under the basic ratio that equates the polyester of anaerobically biodegradable of the present invention, and is incorporated in the polyester polymers with its corresponding residue.They can be randomly extra hydroxycarboxylic acid or its form polyester derivative in the presence of prepare.Therefore the present invention contains the diacid residues (100 moles of %) and the diol residue (100 moles of %) of first-class substantially molar ratio derived from the polyester of dicarboxylic acid and diol residue, makes the total mole number of repeating unit equal 100 moles of %.Can come this polyester of modification by introducing hydroxycarboxylic acid, and not influence these 100 moles of % sums (being that hydroxycarboxylic acid does not enter this 100 moles of % countings) because it has contained the stoichiometric balance of acid and oh group.
The molecular fraction of the diacid of present disclosure is expressed as the mark (or percentage ratio) of the total mole number of diacid residues in any concrete polymer samples.For example, the copolyesters that contains 60 moles of % hexanodioic acids based on total diacid residues refers to that copolyesters contains 60 moles of % hexanodioic acid residues in amounting to 100 moles of % diacid residues.Therefore, in per 100 mole of diacid residues, there is 60 moles hexanodioic acid residue.
Similarly, the molecular fraction of glycol is expressed as the mark (or percentage ratio) of the total mole number of diol residue in polymer samples.For example, the copolyesters that contains 15 moles of % ethylene glycol based on total diol residue refers to that copolyesters contains 15 moles of % glycol residues in amounting to 100 moles of % diol residue.Therefore, in per 100 moles of diol residue, there is 15 moles glycol residue.
The molecular fraction of the hydroxycarboxylic acid of this paper is expressed as the mark (or percentage ratio) of the total mole number of diacid residues in polymer samples.For example, the polymkeric substance that contains 10 moles of % hydroxycarboxylic acids, 60 moles of % hexanodioic acids, 40 moles of % terephthalic acids and 100 moles of % butyleneglycols refers to that the hydroxycarboxylic acid residue mole number in this sample is 1/10th of a diacid residues mole number in this sample (being that hexanodioic acid residue mole number adds terephthalic acid residue's mole number in the case).Therefore, under the situation of the multipolymer that contains hydroxycarboxylic acid, total mole of % of all components adds up greater than 200 (x mole % hydroxycarboxylic acids+100 moles of % diacid+100 mole % glycol).
Anaerobically biodegradable polyester of the present invention can comprise the residue of one or more non-aromatic dicarboxylic acids.The example of non-aromatic dicarboxylic acid comprises pentanedioic acid and hexanodioic acid.
Unless beyond the aromatic dicarboxylic acid, the anaerobically biodegradable polyester can comprise the aromatic dicarboxylic acid residue.The example of the aromatic dicarboxylic acid that is suitable for comprises terephthalic acid, m-phthalic acid, 5-sulfoisophthalic acid and 2,6-naphthalene dicarboxylic acids.In one embodiment, the terephthalic acid that aromatic dicarboxylic acid comprises, wherein at the most the terephthalic acid of 5 moles of % by m-phthalic acid, 5-sulfoisophthalic acid and 2, one or more displacements in the 6-naphthalene dicarboxylic acids.
The amount of aromatic dicarboxylic acid residue in polyester of the present invention is for making the under anaerobic biodegradable significant quantity of this polyester.Accurately amount depends on the concrete combination of the aromatics and non-aromatic dicarboxylic acid and glycol and the hydroxycarboxylic acid that are used to prepare polyester.Usually, the aliphatic-aromatic polyesters that contains the aromatic dicarboxylic acid residue (calculating based on the total mole number of diacid residues in the polyester) of the about 43 moles of % of the 39-that has an appointment can be an anaerobically biodegradable by expection.The aliphatic-aromatic polyesters that contains the aromatic dicarboxylic acid residue (total mole number based on diacid residues in the polyester calculates) of the about 42 moles of % of the 40-that has an appointment can be an anaerobically biodegradable by expection also.When with usually easy biodegradable material such as thermoplastic starch compound tense, can expect that the scope of the extra aromatic dicarboxylic acid residue that obtains the anaerobically biodegradable polymer blend comprises about 46 moles of % of about 39-and the about 43 moles of % of about 41-.
The example that is applicable to the glycol of polyester of the present invention includes, but is not limited to ethylene glycol, Diethylene Glycol, propylene glycol, 1, ammediol, 2,2-dimethyl-1, ammediol, 1,3 butylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, polyoxyethylene glycol, Diethylene Glycol, 2,2,4-trimethylammonium-1, the 6-hexylene glycol, thiodiethanol, 1, the 3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 2,2,4,4-tetramethyl--1,3-cyclobutanediol, triethylene glycol and TEG, preferred glycol comprises that one or more are selected from ethylene glycol, Diethylene Glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, glycol with 1,4 cyclohexane dimethanol.In one embodiment, polyester of the present invention comprises 1 of the about 100 moles of % of about 85-, the residue of 4-butyleneglycol residue and about 15 another glycol of molar percentage of about 0-.In another embodiment, polyester comprises 1 of about 100 moles of %, 4-butyleneglycol residue.
Anaerobically biodegradable polyester of the present invention can be easily adopts common polycondensation condition preparation by suitable dicarboxylic acid, ester, acid anhydrides or salt, suitable glycol or diol mixture and any branching agent.Can prepare by continuous, semicontinuous and gap operating pattern, and can adopt a variety of type of reactor.Suitable type of reactor includes but not limited to stirred pot, continuously stirring jar, slurry, tubular type, scraped film type, falling film type or extrusion reaction device.
Anaerobically biodegradable polyester of the present invention can be by the known operation preparation of one skilled in the art, and it for example is described in the United States Patent (USP) 2012267.These reactions usually under 150 ℃ of-300 ℃ of temperature, polycondensation catalyst for example alkoxy titanium compound, alkali metal hydroxide and alcoholate, organic carboxyl acid salt, Alkyzin compound, metal oxide etc. in the presence of carry out.The common consumption of catalyzer is 10-1000ppm, based on the reaction reagent total weight.
Can come modified poly ester by the hydroxycarboxylic acid residue (total mole number based on diacid residues calculates) that is introduced into many about 15 moles of %.(1) aliphatic diacid residue; (2) be different from 1, the diacid residues of 4-butyleneglycol (if the words that have); (3) total mole of % of hydroxycarboxylic acid residue (if the words that have) is less than about 65 ideally.In other embodiments, total mole of % scope of (1)+(2)+(3) is about 65 for about 50-, and about 55-is about 62, or about 58-about 62.
Suitable hydroxycarboxylic acid example comprises gamma-butyrolactone; Caprolactone; Lactic acid (D or L-type or its mixture); The aliphatic hydroxide radical alkylide comprises 4 hydroxybutyric acid, 4-hydroxypentanoic acid, diethoxalic acid and 4-Hydroxyoctanoic acid; And be applicable to the preparation polyester derivative.These hydroxycarboxylic acids direct reaction by conventional methods enter polyester and are introduced into, become ester derivative with its free sour form or other, for example its ester (comprising the cyclic ester that is called lactone) reacts, or by with it with polymerized form and above pet reaction blend, described polymerized form for example polyhydroxyalkanoatefrom (PHAs) as poly butyric ester (PHB), poly butyric ester-altogether-valerate (PHBv), poly butyric ester-altogether-octanoate (PHBO) and poly butyric ester-be total to-capronate (PHBHx); Polycaprolactone (PCL) and poly(lactic acid) (PLA) are from synthetic or natural origin.
Described anaerobically biodegradable polyester can comprise about 1000 repeating units of about 10-, also can comprise about 600 repeating units of about 15-.The anaerobically biodegradable polyester can have the limiting viscosity of the about 2.0dL/g of about 0.4-, the limiting viscosity of the about 1.4dL/g of perhaps about 0.7-, the concentration of 0.5g polyester records in the phenol/tetrachloroethane solution that adopts under 25 ℃ the temperature in 40/60 (weight) of 100ml.
The anaerobically biodegradable polyester can be chosen the residue that contains branching agent wantonly.The weight percentage scope of branching agent is the about 2wt% of about 0-, and the about 1wt% of about 0.1-, or the about 0.5wt% of about 0.1-are based on the polyester total weight.This branching agent preferably has about 50 to about 5000, or about 92 to about 3000 weight-average molecular weight, and has about 3 to about 6 functionality.For example, branching agent can be the polyvalent alcohol with 3 to 6 hydroxyls, has the poly carboxylic acid (or its one-tenth ester equivalent) of 3 or 4 carboxyls or has altogether the alcohol ester residue of 3 to 6 hydroxyls and carboxyl.
Can comprise glycerine, TriMethylolPropane(TMP), trimethylolethane as the representative low molecular weight polyols of branching agent, polyether triol, glycerine, 1,2,4-trihydroxybutane, tetramethylolmethane, 1,2, the 6-hexanetriol, Sorbitol Powder, 1,1,4,4-four (methylol) hexanaphthene, three (2-hydroxyethyl) isocyanuric acid ester and Dipentaerythritol.The more concrete branching agent example of high molecular weight polyols (MW 400-3000) is the triol that is obtained by the alkylene oxide with 2-3 carbon atom such as oxyethane and propylene oxide and polyol initiator condensation.
The representational polycarboxylic acid that can be used as branching agent comprises that benzene connects tricarboxylic acid, trimellitic acid (1,2, the 4-benzene tricarboxylic acid) and acid anhydride, trimesic acid (1,3,5-benzene tricarbonic acid), Pyromellitic Acid and acid anhydride, benzene tertacarbonic acid, benzophenone tetracarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,1,2-ethane tricarboxylic acid, 1,3,5-pentane tricarboxylic acid and 1,2,3,4-pentamethylene tetracarboxylic acid.Although described acid can be used as it is, also use its lower alkyl esters or its cyclic anhydride form (under the situation that can form cyclic anhydride).
Representational " branched hydroxyl carboxylic acid " (difference of the hydroxycarboxylic acid that other place is mentioned in these hydroxycarboxylic acids and this specification sheets is not contain the acid and the oh group of equal number, and gets rid of outside other the local hydroxycarboxylic acid definition used of this specification sheets) as branching agent comprises oxysuccinic acid, citric acid, tartrate, 3-hydroxyl pentanedioic acid, glactaric acid, trihydroxy glutaric acid, 4-carboxyl Tetra hydro Phthalic anhydride, hydroxyl m-phthalic acid and 4-(beta-hydroxyethyl) phthalic acid.This branched hydroxyl carboxylic acid comprises the combination of 3 or a plurality of hydroxyl and carboxyl.Representational branching agent comprises trimellitic acid, trimesic acid, tetramethylolmethane, TriMethylolPropane(TMP) and 1,2,4-trihydroxybutane.
Anaerobically biodegradable polyester of the present invention can comprise that also one or more contain the ionic monomer to increase its melt viscosity.Contain the salt or derivatives thereof that the ionic monomer can be selected from sulfoisophthalic acid.The monomeric representative instance of this class is a sodium for sulfoisophthalic acid or the sodium dimethyl ester for sulfoisophthalic acid.The described monomeric concentration of ionic that contains is about 5.0% mole of the about 0.3%-that accounts for the diacid residues total mole number, about 2.0% mole of more preferably about 0.3%-.
It is one or more chainextenders of the about 5wt% of 0%-that anaerobically biodegradable polyester of the present invention also can comprise based on the polyester gross weight.Exemplary chainextender is for for example those are disclosed in the divinyl ether of US5817721 or for example those are disclosed in the vulcabond of US 6303677.Representational divinyl ether has 1,4-butyleneglycol divinyl ether, 1,5-hexylene glycol divinyl ether and 1,4 cyclohexane dimethanol divinyl ether.Representational vulcabond has toluene 2,4-vulcabond, toluene 2,6-vulcabond, 2,4 '-diphenylmethanediisocyanate, naphthalene-1,5-vulcabond, Xylene Diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and methylene radical two (2-isocyanato-hexanaphthene).The weight percentage ranges that is suitable for is for to be calculated as about 3.5wt% of about 0.3%-and the about 2.5wt% of about 0.5%-based on this polyester total weight percent.Also can use functionality to be no less than 3 in principle, can comprise the isocyanate compound of trifunctional of isocyanuric acid ester and/or connection urea groups, perhaps with triisocyanate or polyisocyanic acid ester moiety displacement diisocyanate cpd.
Polyester of the present invention can with the thermoplastic starch blend to form the anaerobically biodegradable composition.The amount of thermoplastic starch in composition can be about 70 weight percents of about 5-based on composition weight.Expection and thermoplastic starch blend will increase the biodegradation rate of polyester.
The theme that more comes into one's own in recent years is the blend of starch and synthetic polymer such as polyethylene (PE) and polypropylene (PP).This motivation is an intensive, because starch is abundant and cheap filler material.And starch gives the enhanced biodegradable also can for the gained blend.Yet these PE and PP polymkeric substance also are not suitable for some application, as the biodegradable completely situation of needs.
The native starch of finding in plant product can be used as granular powder and separates.Native starch can add the water of limited amount under High Temperature High Pressure handles to form melt.This melt is called gelling or modified starch.Modified starch can mix with the additive of for example softening agent to obtain thermoplastic starch or TPS.These starch forms can be mixed with polyester of the present invention, by adopt routine techniques for example technology described in the United States Patent (USP) 5095054 and 5362777 carry out; Its full content is introduced as reference.
Except TPS or replace TPS, polyester of the present invention also can with the inorganic salt combination to form the anaerobically biodegradable composition.Said composition can comprise the inorganic salt at least about 0.1 weight percent.The limiting examples of inorganic salt comprise metal carbonate, metal oxide, metal phosphate, metal chloride, metal sulfate, and composition thereof.Representative metallic cation in these inorganic salt can comprise calcium, potassium, sodium, magnesium, other I family and II family metallic cation, aluminium, titanium and silicon.Representational inorganic salt comprise talcum, lime carbonate, magnesiumcarbonate, salt of wormwood, yellow soda ash, calcium chloride, magnesium chloride, calcium phosphate, titanium dioxide, silicon oxide, aluminum oxide, and composition thereof.Usually, the inorganic salt content scope is the about 60wt% of about 0.1-, the about 50wt% of about 1-, or the about 40wt% of about 2-.In one embodiment, this anaerobically biodegradable composition comprises lime carbonate or the talcum of the about 20wt% of about 1-.
Randomly, one or more additives being introduced anaerobically biodegradable composition of the present invention also is ideal.Suitable additive comprise (but being not limited to) processing aid, weighting agent, tensio-active agent, softening agent, expanding material, anti-impact modifier, nucleator, antioxidant, heat or ultra-violet stabilizer, tinting material, static inhibitor, lubricant, whipping agent, dispersion agent, thickening material, antiseptic-germicide, and composition thereof.Usually, these additives account for about at the most 10wt% of the present composition, about at the most 20wt%, or about at the most 30wt%.
By ordinary method, polyester of the present invention and composition can be made into useful article of manufacture.These goods confirmed its part anaerobism (hypoxemia) or fully anaerobic condition down novelty become the ability of carbonic acid gas, water and biomass with mineralising subsequently with unexpected capacity of decomposition.Therefore, the present invention not only comprises polyester and the composition that this uniqueness is useful, also comprises the article of manufacture by they preparations.Possible goods comprise; but be not limited to, film, molten blow binding agent that screen cloth, nonwoven fabric, conjugate fiber component, adhesion-promoting layer, Mierocrystalline cellulose use, can break up non-woven fabric and film, solubilized binder fiber, protective layer and be used for the carrier that activeconstituents discharges or is dissolved in the water.Other can extrude with the melt spun fibre material also be feasible.
The processing technology that is used to produce end article includes, but not limited to moltenly blow, founding, compacting and spunbond.Can adopt conventional connection and building mode (for example to pass through the solvent or the tackiness agent combination of suitable solvent or binding system, randomly unite pressure or hot laminating, coextrusion technology, or the combination of the combination/interconnection technique of other routine that adopts in the industry) independent component structure is further merged to obtain the resultant articles structure.
Polyester of the present invention and composition are particularly useful for disposable absorbent article.Term used herein " absorbing products " refers to absorb the also goods of receiving body fluids, and more specifically refers to pasting or contiguous wearer's body placement, to absorb and to hold the goods of the various liquid of health discharge.In addition, term " disposable absorbent article " refer to single use the goods that the back plans to abandon (be that whole primary absorbing products is not planned to be cleaned or recovered or reuse as absorbing products, although some material or all absorbing products can be recovered, reuse, compost or break up).The present invention is applicable to various absorbing products, for example diaper, incontinence panty girdle, incontinence pad, slacks, degree of tightness (pull-on) diaper, diaper liner, menstruation pad, cotton wool, protection pad, interlabial parts, cotton balls, facial tissue, paper handkerchief, chest pad, or the like, and other can break up object, for example cotton balls applicator assembly (comprising socket and piston), cotton balls core, wrapping material and be used for the packing of various products, comprise disposable absorbent article, disposable glove, or the like.
These absorbing products generally include the fluid-tight substantially primer (backsheet) by membrane prepare of the present invention, the fluid-tight substantially quilting material that is connected in or otherwise links to each other, and the absorbent core between primer and quilting material with primer.Quilting material is adjacent to the surface towards health of absorbent core.Quilting material can be connected to absorbent core and primer by those adhering mode well known in the art.Term used herein " connection " comprises wherein by element is directly invested other element and element directly to be fixed to the structure of other element and wherein by element being invested intermediary element (itself and then invest other element) and element is fixed to indirectly the structure of other element.In some absorbing products, quilting material and primer are connected to each other directly in its periphery.Thereby quilting material also can be directly connected to absorbent core by attachment device with primer and be connected together indirectly.
Invention is illustrated further by the following examples and describe.
Embodiment
Embodiment 1-microorganic adhesion and rupture Analysis
Adopt the conventional blown film processing units among the Technical Service Laboratory of Eastman Chemical Company to prepare film by following mixture, hexanodioic acid and terephthalic acid are as 1 of diacid component and 100 moles of % in this mixture, and the 4-butyleneglycol is as diol component.Terephthaldehyde's acid content and film composition are described in the table 1.
For the film of describing in the table 1, base resin is fed 2-1/2 " single screw extrusion machine, this forcing machine has 24: 1 length: the diameter ratio, and adopt moderate shear, the general purpose polyester screw rod does not mix and 3: 1 compression ratios.In first being processed, resin in dryer dry 8 hours in 150 .Processing additive similarly is dried and by adopting the weight feed system to be delivered to single screw rod expressing technique in first being processed.Processing additives and their ultimate density also are shown in table 1 in the film.The introducing of additive is to adopt to add an amount of 50wt%CaCO in the resin identical with base resin
3Enriched material or in the resin identical, add an amount of 50wt% talcum enriched material and finish with base resin.
Melt is sent by 6-inch individual layer, spiral axle center die head subsequently.The double flange air ring that adopts frozen air and do not have an inner bubbling cooling (internal bubble cooling) prepares and has 2: 1 laterally/vertically films of blow-up ratios.The employing framework (collapsing frame) that subsides is 18 feet highly, tubular membrane is subsided prepare this film.Shown the temperature distribution that is used to process this film in the table 3.
Acquisition is by the commercial membranes of other anaerobically biodegradable polymer manufacture and be described in the table 2.
All films all place septic tank (part anaerobism) environment of running.After 3 months, fetch each film and estimate microorganic adhesion and the disruptive degree.
As used in the table, " T " refers to that terephthalic acid and " TPS " refer to thermoplastic starch.
The film of table 1-Eastman preparation
| Film ID No. | Film is formed | Film thickness (mil) | Microorganic adhesion | Break |
| 1 | 43mol%T w/10wt% talcum | 1.45 | Fabulous | Good |
| 2 | 45mol%T w/10wt% talcum | 1.25 | Relatively good | Very poor |
| 3 | 48mol％T w/15wt％CaCO 3 | 1.20 | Do not have | Do not have |
Table 2-commercial membranes
| Film ID No. | Film is formed | Film thickness (mil) | Microorganic adhesion | Break |
| 4 | Ecoflex BAG(-47mol％T) w/30wt％TPS | 1.45 | Very poor | Do not have |
| 5 | Belgian Competitor(-47mol％T) w/30wt％TPS | 1.45 | Do not have | Do not have |
Table 3-blown film processing conditions
| Forcing machine zone 1 | 150℃(300) |
| Forcing machine zone 2 | 150℃(300) |
| Forcing machine zone 3 | 155℃(310) |
| Forcing machine zone 4 | 160℃(320) |
| Shifting coupling | 135℃(280) |
| Module | 135℃(280) |
| Counterdie | 135℃(280) |
| Patrix | 135℃(280) |
| The die clearance | 0.030 inch |
| The compression ring temperature | 10℃(50) |
From table 1 and 2 as can be seen, by containing 100mol%1,4-butyleneglycol, the film that is lower than the 45mol% terephthalic acid and is higher than the aliphatic-aromatic copolyesters preparation of 55mol% hexanodioic acid all are proved fabulous microorganic adhesion and film rupture.By containing 100mol%1,4-butyleneglycol, the film that is higher than the 45mol% terephthalic acid and is lower than the aliphatic-aromatic copolyesters preparation of 55mol% hexanodioic acid demonstrate adhering to of minimum degree and break.By containing 100mol%1,4-butyleneglycol, 46-7mol% terephthalic acid and 53-4mol% hexanodioic acid and the bag that is purchased that has added the aliphatic-aromatic copolyesters preparation of high-content (30wt%) thermoplastic starch do not demonstrate and adhere to or break.
No matter the complete biodegradable under aerobic still is anaerobism (or between between the two) condition makes the carbon of material be become microorganism cells matter and the final carbonic acid gas that forms by biological degradation.And, although the minimizing of tensile strength, elongation molecular weight or oxygen-consumption or quality may hint biological degradation, have only final formation carbonic acid gas just to be known as the complete biodegradable of having indicated in aerobic and anaerobic biodegradation.
Embodiment 2-radiochemical analysis
Film formation process:
Adopt the aliphatic-aromatic polyesters resin (mark on aromatic ring carbon) of the synthetic three kinds of carbon-14 marks of terephthalic acid of carbon-14 mark.The composition and the method that are used to prepare film are described below.
Reactor charging (50ml round bottom 24/40STG)
1.3.92g dimethyl terephthalate (DMT) (DMT) is used for 42 moles of %T;
4.01g DMT is used for 43 moles of %T; Or
4.32g DMT is used for 46 moles of %T
2.4.3136g hexanodioic acid
3.8.0698g 1, the 4-butyleneglycol
4.0.10ml the Ti catalyzer of 1.02w/vol% in BuOH
5.0.004g the DMT of C-14 mark (Lot#NEN2922-135) is used for 42mol%T;
0.005g the DMT of C-14 mark (Lot#NEN2922-135) is used for 43mol%T; Or
0.005g the DMT of C-14 mark (Lot#NEN2922-135) is used for 46mol%T;
6.6.1mg the Ultranox 626 that sizes mixing in the 0.5ml butyleneglycol increases temperature to 255 ℃ subsequently
Operation
1. article 1,2,3,4 and 5 flasks of packing into; Use N
2Break up and vacuumize with vacuum pump; Break up 2 times.
2. with following temperature and time heating flask:
The temperature ℃ time
190 1hr.
200 1hr.
210 1.5hr.
Add Ultranox 626 (article 6)
The slight vacuum of 255 30min. at the most
Violent agitation
Vacuum is increased to 0.11 holder
High temperature, high vacuum 1.5hr.
Polymkeric substance has light amber and viscosity and is increased to and makes its parcel agitator and break away from from flask walls.The polymer material top has because typical whirlpool or the ripple that high viscosity produces.
3. vacuum is replaced by nitrogen, and metal bath reduces, and reaction flask is by the room air cooling and subsequently by water cooling (30min.).
4. after the polymkeric substance sclerosis, flask enters hot metal bath and " stretching " (2min.).
5. revolving stirrer cools off (30min.) fully up to polymkeric substance.
With glass cutter perpendicular to cut around the circumference of flask neck, with hot granulated glass sphere it is split, separate the agitator that two halves will adhere to polymkeric substance and discharge.
Three kinds of resins of gained contain the 42 moles of % terephthalic acids of having an appointment, 43 moles of % terephthalic acids and 46 moles of % terephthalic acids.Adopt proton N MR to measure terephthalic acid mole % (replicate analysis).Resin sample is stored under nitrogen in 0-2 ℃ siccative, up to being dissolved in 1: 3 methyl alcohol: in the dichloromethane solvent mixture.Sample by solvent cast to the teflon lining plank and cut into 1 * 2 inch strip.Thickness is controlled than the amount of solvent by the polyester of toppling over onboard.Cutting 6 films is 1.0 mils ± 0.2 mil to keep final thickness.Every film is represented 0.4 hundred ten thousand decays/minute (dpm) ± 1500dpm (dpm refers to the radiocounting for the per minute of collected background adjusting of this time period).
The radiological chemistry test step
Adopt the improvement operation of ASTM D6340-98 standard method, preparation 500 gram compost also add the 2L reactor.The restriction air-flow is so that this compost at room temperature becomes little aerobic in two weeks.Each film is added this little aerobic compost, make air admission amount minimum, and and compost thorough mixing.In case after mixing, sealed vessel and this mixing tank do not re-use in test.The air of bubbling by water reservoir with 400cc/min " break up " join still at the bottom of, continue cycles in 24 90 seconds/weeks.With Desmycosin quality controller control air-flow with Camile reference.Waste gas from compost is passed through two successive container for capturing by bubbling, is used for CO
2The post #1 of Carbosorb E and post #2 subsequently.Counting representative in post 2 is captive C in first post not
14-CO
2The efficient of post is shown in following table 4.
Table 4
| The timed interval | Post #1 | Post #2 |
| 4 hours dpm | 138,881 | 0 |
| 6 hours dpm | 283,425 | 511 |
| 8 hours dpm | 114,044 | 560 |
Test total dpm counting that Carbosorb catches weekly.The accumulation % of sum is calculated as follows: (this week grand total-last week counting)/(grand total in the original membrane).Optionally extra Carbosorb is added this ravin.Material in the ravin remains in the liquid neutralization by per 30 days adding 100cc septic tank effluents and is in the living microorganism state.
Equipment therefor is consistent with the D6340-98ASTM method with method, and different is following change:
1. limit air-flow as mentioned above;
2. add the septic tank effluent as mentioned above; With
3. adopt the environment room temp to replace 58 ℃ of temperature that adopt in this method, this is used to simulate the active compost above 1 ton.
The biological degradation cumulative percentage (calculate as above) of three kinds of films during 180 days is shown in following table 5.Find out that from data biological degraded surpassed 5% to three kinds of all films at 120 days, surpassed 10% at 150 days.In the same period, the film that contains 42 moles of % terephthalic acids than the film that contains 46 moles of % terephthalic acids with the fast speeds biological degradation and reach bigger degree.
Table 5
| My god | Total biological degradation per-cent | ||
| 46％T | 44％T | 43％T | |
| 0 | 0.16 | 0.14 | 0.14 |
| 7 | 0.16 | 0.15 | 0.31 |
| 14 | 0.16 | 0.15 | 0.49 |
| 21 | 0.16 | 0.16 | 0.96 |
| 28 | 0.19 | 0.31 | 1.15 |
| 35 | 0.41 | 0.78 | 1.94 |
| 42 | 0.45 | 1.09 | 2.59 |
| 49 | 0.49 | 1.19 | 3.07 |
| 56 | 0.95 | 1.33 | 4.25 |
| 63 | 1.22 | 2.14 | 4.98 |
| 70 | 1.39 | 3.06 | 5.31 |
| 77 | 1.63 | 4.52 | 6.64 |
| 84 | 1.99 | 4.97 | 7.36 |
| 91 | 2.58 | 5.81 | 9.03 |
| 98 | 2.97 | 7.07 | 10.21 |
| 105 | 3.65 | 8.32 | 12.11 |
| 112 | 4.42 | 9.51 | 13.78 |
| 119 | 5.74 | 10.85 | 15.41 |
| 126 | 6.9 | 12.98 | 18.23 |
| 133 | 7.59 | 15.11 | 21.06 |
| 140 | 8.99 | 18.26 | 24.48 |
| 147 | 10.31 | 21.18 | 27.35 |
| 154 | 11.78 | 23.88 | 29.69 |
| 161 | 13.46 | 26.46 | 31.86 |
| 168 | 15.47 | 28.39 | 34.7 |
| 175 | 17.49 | 31.24 | 37.66 |
Claims (45)
1. aliphatic-aromatic polyesters, the amount of the aromatic monomer that it comprises effectively make polyester generation anaerobically biodegradable.
2. the aliphatic-aromatic polyesters of claim 1, wherein said aromatic monomer comprises the terephthalic acid residue, the terephthalic acid residue of 5 moles of % is by derived from m-phthalic acid, 5-sulfoisophthalic acid and 2 at the most, the displacement of the aromatic dicarboxylic acid residue of 6-naphthalene dicarboxylic acids equals 100 moles of % based on the molecular fraction of all diacid residues in the polyester and calculates.
3. the aliphatic-aromatic polyesters of claim 2, it comprises the terephthalic acid residue of about 43 molar percentages of about 39-, equals 100 moles of % based on the molecular fraction of all diacid residues in the polyester and calculates.
4. the aliphatic-aromatic polyesters of claim 3, it comprises the terephthalic acid residue of about 42 molar percentages of about 40-, equals 100 moles of % based on the molecular fraction of all diacid residues in the polyester and calculates.
5. the aliphatic-aromatic polyesters of claim 1, it comprises diol residue, diol residue comprises 1 of about 100 molar percentages of about 85-, 4-butyleneglycol and about 15 molar percentages of about 0-be selected from ethylene glycol, Diethylene Glycol and 1, the diol residue of ammediol equals 100 moles of % based on the molecular fraction of all diol residue in the polyester and calculates.
6. the aliphatic-aromatic polyesters of claim 1, it comprises the hydroxycarboxylic acid residue of about at the most 15 moles of %, equals 100 moles of % based on the molecular fraction of all diacid residues in the polyester and calculates.
7. the aliphatic-aromatic polyesters of claim 6, wherein said hydroxycarboxylic acid are derived from by following material: gamma-butyrolactone, caprolactone, lactic acid, 4 hydroxybutyric acid, 4-hydroxypentanoic acid, diethoxalic acid, 4-Hydroxyoctanoic acid, poly butyric ester, poly butyric ester-altogether-valerate, poly butyric ester-altogether-octanoate, poly butyric ester-altogether-capronate, polycaprolactone and poly(lactic acid).
8. the polyester of an anaerobically biodegradable, it comprises:
(a) diacid residues comprises the non-aromatics dicarboxylic acid residue of aromatic dicarboxylic acid residue He about 61 molar percentages of about 57-of about 43 molar percentages of about 39-; With
(b) diol residue comprises 1 of about 100 molar percentages of about 85-, another diol residue of 4-butyleneglycol and about 15 molar percentages of about 0-;
The molecular fraction that equals all diol residue in 100 moles of % and the polyester based on the molecular fraction of all diacid residues in the polyester equals 100 moles of % and calculates.
9. the polyester of the anaerobically biodegradable of claim 8, wherein said aromatic dicarboxylic acid is selected from terephthalic acid, m-phthalic acid, 5-sulfoisophthalic acid and 2, at least a in the 6-naphthalene dicarboxylic acids.
10. the polyester of the anaerobically biodegradable of claim 8, wherein said non-aromatic dicarboxylic acid are selected from least a in pentanedioic acid and the hexanodioic acid.
11. the polyester of the anaerobically biodegradable of claim 8, wherein said glycol are selected from ethylene glycol, Diethylene Glycol, 1, ammediol, 1,5-pentanediol, 1, at least a in 6-hexylene glycol and the 1,4 cyclohexane dimethanol.
12. the polyester of the anaerobically biodegradable of claim 8, wherein diacid residues comprises the non-aromatics dicarboxylic acid residue of aromatic dicarboxylic acid residue He about 60 molar percentages of about 58-of about 42 molar percentages of about 40-.
13. the polyester of the anaerobically biodegradable of claim 8, wherein said aromatic dicarboxylic acid is a terephthalic acid, and wherein at the most the terephthalic acid of 5 moles of % by m-phthalic acid, 5-sulfoisophthalic acid, or 2, the displacement of 6-naphthalene dicarboxylic acids.
14. the polyester of the anaerobically biodegradable of claim 8, it further comprises the hydroxycarboxylic acid residue of about at the most 15 moles of %, based on the total mole number calculating of diacid residues.
15. the polyester of the anaerobically biodegradable of claim 14, wherein said hydroxycarboxylic acid are derived from following material: gamma-butyrolactone, caprolactone, lactic acid, 4 hydroxybutyric acid, 4-hydroxypentanoic acid, diethoxalic acid, 4-Hydroxyoctanoic acid, poly butyric ester, poly butyric ester-altogether-valerate, poly butyric ester-altogether-octanoate, poly butyric ester-altogether-capronate, polycaprolactone and poly(lactic acid).
16. the polyester of an anaerobically biodegradable, it comprises:
(a) diacid residues comprises the terephthalic acid residue of about 43 molar percentages of about 39-and the hexanodioic acid residue of about 61 molar percentages of Yue 57-; With
(b) diol residue comprises 1 of about 100 molar percentages, 4-butyleneglycol residue;
The molecular fraction that equals all diol residue in 100 moles of % and the polyester based on the molecular fraction of all diacid residues in the polyester equals 100 moles of % and calculates.
17. the polyester of the anaerobically biodegradable of claim 16, wherein diacid residues comprises the terephthalic acid residue of about 42 molar percentages of about 40-and the hexanodioic acid residue of about 60 molar percentages of Yue 58-.
18. the polyester of an anaerobically biodegradable, it comprises:
(a) diacid residues comprises the terephthalic acid residue of about 43 molar percentages of about 39-and the pentanedioic acid residue of about 61 molar percentages of Yue 57-; With
(b) diol residue comprises 1 of about 100 molar percentages, 4-butyleneglycol residue;
The molecular fraction that equals all diol residue in 100 moles of % and the polyester based on the molecular fraction of all diacid residues in the polyester equals 100 moles of % and calculates.
19. the polyester of the anaerobically biodegradable of claim 18, wherein diacid residues comprises the terephthalic acid residue of about 42 molar percentages of about 40-and the pentanedioic acid residue of about 60 molar percentages of Yue 58-.
20. an anaerobically biodegradable composition comprises:
(I) polyester, it comprises:
(a) diacid residues comprises the non-aromatics dicarboxylic acid residue of aromatic dicarboxylic acid residue He about 61 molar percentages of about 54-of about 46 molar percentages of about 39-; With
(b) diol residue comprises 1 of about 100 molar percentages of about 85-, another diol residue of 4-butyleneglycol residue and about 15 molar percentages of about 0-;
The molecular fraction that equals all diol residue in 100 moles of % and the polyester based on the molecular fraction of all diacid residues in the polyester equals 100 moles of % and calculates; With
(II) thermoplastic starch.
21. the composition of the anaerobically biodegradable of claim 20, wherein said aromatic dicarboxylic acid are selected from terephthalic acid, m-phthalic acid, 5-sulfoisophthalic acid and 2,6-naphthalene dicarboxylic acids.
22. the composition of the anaerobically biodegradable of claim 20, wherein said non-aromatic dicarboxylic acid is selected from pentanedioic acid and hexanodioic acid.
23. the composition of the anaerobically biodegradable of claim 20, wherein said glycol are selected from ethylene glycol, Diethylene Glycol, 1, ammediol, 1,5-pentanediol, 1,6-hexylene glycol and 1,4 cyclohexane dimethanol.
24. the composition of the anaerobically biodegradable of claim 20, wherein diacid residues comprises the non-aromatics dicarboxylic acid residue of aromatic dicarboxylic acid residue He about 59 molar percentages of about 57-of about 43 molar percentages of about 41-.
25. the composition of the anaerobically biodegradable of claim 20, wherein said aromatic dicarboxylic acid is a terephthalic acid, and wherein the terephthalic acid of 5 moles of % is by m-phthalic acid, 5-sulfoisophthalic acid or 2 at the most, and the 6-naphthalene dicarboxylic acids is replaced.
26. the composition of the anaerobically biodegradable of claim 20, it comprises the thermoplastic starch of about 70 weight percents of about 5-.
27. the composition of the anaerobically biodegradable of claim 20, it further comprises the inorganic salt of about 60 weight percents of about 0.1-, and inorganic salt comprise the metal ion that is selected from calcium, magnesium, sodium, potassium, titanium, silicon and aluminium.
28. the composition of the anaerobically biodegradable of claim 27, wherein inorganic salt be selected from talcum, lime carbonate, magnesiumcarbonate, salt of wormwood, yellow soda ash, calcium chloride, magnesium chloride, calcium phosphate, titanium dioxide, silicon oxide, aluminum oxide, and composition thereof.
29. the composition of the anaerobically biodegradable of claim 20, it further comprises processing aid, weighting agent, tensio-active agent, softening agent, expanding material, anti-impact modifier, nucleator, antioxidant, heat or ultra-violet stabilizer, tinting material, static inhibitor, lubricant, whipping agent, dispersion agent, thickening material, antiseptic-germicide or its mixture.
30. the composition of the anaerobically biodegradable of claim 20, wherein this polyester further comprises the hydroxycarboxylic acid residue of about at the most 15 moles of %, calculates based on the diacid residues total mole number.
31. the composition of the anaerobically biodegradable of claim 30, wherein said hydroxycarboxylic acid are derived from following material: gamma-butyrolactone, caprolactone, lactic acid, 4 hydroxybutyric acid, 4-hydroxypentanoic acid, diethoxalic acid, 4-Hydroxyoctanoic acid, poly butyric ester, poly butyric ester-altogether-valerate, poly butyric ester-altogether-octanoate, poly butyric ester-altogether-capronate, polycaprolactone and poly(lactic acid).
32. an anaerobically biodegradable composition comprises:
(I) polyester, it comprises:
(a) diacid residues comprises the non-aromatics dicarboxylic acid residue of aromatic dicarboxylic acid residue He about 61 molar percentages of about 57-of about 43 molar percentages of about 39-; With
(b) diol residue comprises 1 of about 100 molar percentages of about 85-, another diol residue of 4-butyleneglycol residue and about 85 molar percentages of about 0-;
The molecular fraction that equals all diol residue in 100 moles of % and the polyester based on the molecular fraction of all diacid residues in the polyester equals 100 moles of % and calculates; With
(II) inorganic salt.
33. the composition of the anaerobically biodegradable of claim 32, wherein said aromatic dicarboxylic acid are selected from terephthalic acid, m-phthalic acid, 5-sulfoisophthalic acid and 2,6-naphthalene dicarboxylic acids.
34. the composition of the anaerobically biodegradable of claim 32, wherein said non-aromatic dicarboxylic acid is selected from pentanedioic acid and hexanodioic acid.
35. the composition of the anaerobically biodegradable of claim 32, wherein said glycol are selected from ethylene glycol, Diethylene Glycol, 1, ammediol, 1,5-pentanediol, 1,6-hexylene glycol and 1,4 cyclohexane dimethanol.
36. the composition of the anaerobically biodegradable of claim 32, wherein said diacid residues comprise the non-aromatics dicarboxylic acid residue of aromatic dicarboxylic acid residue He about 60 molar percentages of about 58-of about 42 molar percentages of about 40-.
37. the anaerobically biodegradable polyester of claim 32, wherein said aromatic dicarboxylic acid is a terephthalic acid, and wherein the terephthalic acid of 5 moles of % is by m-phthalic acid, 5-sulfoisophthalic acid or 2 at the most, and the 6-naphthalene dicarboxylic acids is replaced.
38. the composition of the anaerobically biodegradable of claim 32, wherein said inorganic salt be selected from talcum, lime carbonate, magnesiumcarbonate, salt of wormwood, yellow soda ash, calcium chloride, magnesium chloride, calcium phosphate, titanium dioxide, silicon oxide, aluminum oxide, and composition thereof.
39. the composition of the anaerobically biodegradable of claim 32, it further comprises processing aid, weighting agent, tensio-active agent, softening agent, expanding material, anti-impact modifier, nucleator, antioxidant, heat or ultra-violet stabilizer, tinting material, static inhibitor, lubricant, whipping agent, dispersion agent, thickening material, antiseptic-germicide or its mixture.
40. the composition of the anaerobically biodegradable of claim 32, wherein this polyester further comprises the hydroxycarboxylic acid residue of about at the most 15 moles of %, calculates based on the diacid residues total mole number.
41. the composition of the anaerobically biodegradable of claim 40, wherein said hydroxycarboxylic acid are derived from following material: gamma-butyrolactone, caprolactone, lactic acid, 4 hydroxybutyric acid, 4-hydroxypentanoic acid, diethoxalic acid, 4-Hydroxyoctanoic acid, poly butyric ester, poly butyric ester-altogether-valerate, poly butyric ester-altogether-octanoate, poly butyric ester-altogether-capronate, polycaprolactone and poly(lactic acid).
42. an article of manufacture, it comprises the anaerobically biodegradable polyester of claim 8.
43. the article of manufacture of claim 42, it is film, fiber, supatex fabric and tackiness agent.
44. an absorbent article comprises quilting material, primer and the absorption layer between primer and quilting material, wherein at least a portion of quilting material or primer comprises the anaerobically biodegradable polyester of claim 8.
45. a cotton balls applicator assembly, it comprises socket and piston, and wherein at least a portion of socket or piston comprises the anaerobically biodegradable polyester of claim 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55483804P | 2004-03-19 | 2004-03-19 | |
| US60/554,838 | 2004-03-19 | ||
| US10/852,502 | 2004-05-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1976970A true CN1976970A (en) | 2007-06-06 |
Family
ID=38126315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580008900 Pending CN1976970A (en) | 2004-03-19 | 2005-03-10 | Anaerobically biodegradable polyesters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1976970A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759968A (en) * | 2010-03-08 | 2010-06-30 | 林存革 | Biodegradable film and preparation method thereof |
| CN102924882A (en) * | 2012-10-26 | 2013-02-13 | 无锡中易薄膜科技有限公司 | Degradable high polymer film and preparation method thereof |
| WO2013071802A1 (en) * | 2011-10-12 | 2013-05-23 | 苏州莫立克新型材料有限公司 | Fast degradable polyester polymer and preparation method and use thereof |
| CN105153405A (en) * | 2008-05-08 | 2015-12-16 | 诺瓦蒙特股份公司 | Aliphatic-aromatic biodegradable polyester |
| CN109627986A (en) * | 2018-10-15 | 2019-04-16 | 哈尔滨工业大学无锡新材料研究院 | Dedicated degradable adhesive of a kind of glass/metal bonding and preparation method thereof |
| CN114940745A (en) * | 2022-06-09 | 2022-08-26 | 万华化学集团股份有限公司 | Preparation method of polylactic acid with controllable molecular weight |
| CN115806726A (en) * | 2021-09-14 | 2023-03-17 | 南亚塑胶工业股份有限公司 | Degradable environment-friendly polyester film and environment-friendly polyester composition thereof |
-
2005
- 2005-03-10 CN CN 200580008900 patent/CN1976970A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153405A (en) * | 2008-05-08 | 2015-12-16 | 诺瓦蒙特股份公司 | Aliphatic-aromatic biodegradable polyester |
| CN101759968A (en) * | 2010-03-08 | 2010-06-30 | 林存革 | Biodegradable film and preparation method thereof |
| WO2013071802A1 (en) * | 2011-10-12 | 2013-05-23 | 苏州莫立克新型材料有限公司 | Fast degradable polyester polymer and preparation method and use thereof |
| CN102924882A (en) * | 2012-10-26 | 2013-02-13 | 无锡中易薄膜科技有限公司 | Degradable high polymer film and preparation method thereof |
| CN109627986A (en) * | 2018-10-15 | 2019-04-16 | 哈尔滨工业大学无锡新材料研究院 | Dedicated degradable adhesive of a kind of glass/metal bonding and preparation method thereof |
| CN109627986B (en) * | 2018-10-15 | 2021-05-25 | 哈尔滨工业大学无锡新材料研究院 | Degradable adhesive special for glass/metal adhesion and preparation method thereof |
| CN115806726A (en) * | 2021-09-14 | 2023-03-17 | 南亚塑胶工业股份有限公司 | Degradable environment-friendly polyester film and environment-friendly polyester composition thereof |
| CN114940745A (en) * | 2022-06-09 | 2022-08-26 | 万华化学集团股份有限公司 | Preparation method of polylactic acid with controllable molecular weight |
| CN114940745B (en) * | 2022-06-09 | 2024-06-25 | 万华化学集团股份有限公司 | Preparation method of polylactic acid with controllable molecular weight |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1725602A2 (en) | Anaerobically biodegradable polyesters | |
| CN1976970A (en) | Anaerobically biodegradable polyesters | |
| CN110791069B (en) | Full-degradable high-barrier composite material for flexible package | |
| US5219646A (en) | Polyester blends and their use in compostable products such as disposable diapers | |
| US7138439B2 (en) | Biodegradable compounds including poly(lactic acid) polymer compositions and products | |
| CN1204160C (en) | Copolymer resin composition and producing process thereof | |
| JP2003532804A (en) | Copolyester and fibrous material formed therefrom | |
| KR20170110625A (en) | Integrated process for treating recycled streams of pet and ptt | |
| EP1482000A2 (en) | Copolyesters having repeat units derived from succinic acid | |
| CN1898323A (en) | Blends of aliphatic-aromatic copolyesters with ethylene-vinyl acetate copolymers | |
| CN1500114A (en) | Polyhydroxyalkanoate copolymer and polylactic acid polymer compsns. for laminates and films | |
| JPH11511767A (en) | Biologically degradable polymer, process for its production and its use for producing biologically degradable shaped bodies | |
| WO2014019459A1 (en) | Biodegradable copolyester containing 2,5-furandicarboxylate, product thereof, preparation method therefor and use thereof | |
| CN1276807A (en) | Condensation copolymers having surpressed crystallinity | |
| CN1882657A (en) | Poly(3-hydroxyalkanoate) composition and molded object thereof | |
| CN1129005A (en) | Biodegradable compostable plastic and method for making same | |
| CN113773478B (en) | Poly (carbonate-ether) based biodegradable polyester and preparation method thereof | |
| JP2006176757A (en) | Production method for polyester | |
| JP4811772B2 (en) | Biodegradation method of poly-D-hydroxybutyric acid | |
| JP2005097590A (en) | Polyoxalate composition and molded product obtained therefrom | |
| CN113105725A (en) | Biodegradable material and preparation method and application thereof | |
| JP2807399B2 (en) | Soil conditioner | |
| WO1993007198A1 (en) | Sulfonated polyesters and their use in compostable products such as disposable diapers | |
| JP4089575B2 (en) | Cellulose ester composition and molded product obtained therefrom | |
| JP2008063358A (en) | Polyester, method for producing the same and polyester block copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20070606 |