CN101568568A - Processes for manufacturing polyesters from post-consumer polyester - Google Patents
Processes for manufacturing polyesters from post-consumer polyester Download PDFInfo
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- CN101568568A CN101568568A CNA2007800481279A CN200780048127A CN101568568A CN 101568568 A CN101568568 A CN 101568568A CN A2007800481279 A CNA2007800481279 A CN A2007800481279A CN 200780048127 A CN200780048127 A CN 200780048127A CN 101568568 A CN101568568 A CN 101568568A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to processes for manufacturing polyesters. The processes can be used for manufacturing polyesters from post-consumer polyesters. The processes include contacting a post-consumer polyester with at least one diol, at elevated temperature in presence of a catalyst, effecting a transesterification reaction. Biologically-derived diols can be used.
Description
Invention field
The present invention relates to make the method for polyester.Described method especially can be used for making the polyester that attribute and function are substantially similar to new polyester by post-consumer polyester.
Background of invention
Be used on numerous application markets such as polyester such as polyethylene terephthalate (PET) and polybutylene terephthalates, comprise fiber, film and engineering component.Owing to use the annual rubbish that can produce huge amount of these polyester that must abandon.Undoubtedly, abandon and to cause environmental problem.These depleted post-consumer polyesters are reused in expectation.
The ordinary method of recovery polyester relates to separation and purifying comes the dimethyl terephthalate (DMT) (DMT) of autopolyester or the polycondensation of terephthalic acid (TPA) and DMT subsequently or TPA and ethylene glycol.Therefore, reclaim the energy-intensive that becomes, thereby become a kind of extremely expensive method.
Expect method new and/or the useless polyester of improved use.
Summary of the invention
One aspect of the present invention is a method of being made polyester by post-consumer polyester, and described method is included under the temperature of about room temperature to about 300 ℃ of scopes, in the presence of polymerizing catalyst, contacts post-consumer polyester with at least a glycol (for example 1, ammediol).In some preferred embodiments, described catalyst pack stanniferous or titanium.
In some preferred embodiments, post-consumer polyester is an industrial back polyester.
Another aspect of the present invention is the polyester by the preparation of following method, and described method is included in about room temperature to the interior temperature of about 300 ℃ of scopes, in the presence of polymerizing catalyst, makes post-consumer polyester contact at least a glycol.
Detailed Description Of The Invention
In method disclosed herein, saved common separation used in the conventional recovery method and purification step, therefore reduced the manufacturing cost of polymkeric substance.In some embodiments, the polymkeric substance by this approach production can provide the attribute that is similar to new polyester and function and manufacturing cost and energy utilization overall minimizing, reduce the gas purging that can cause Greenhouse effect, thereby reduce the environment footprint.
Unless otherwise defined, the implication of all scientific and technical terminologies used herein and those skilled in the art's common sense is the same.As conflict, the definition included with this specification sheets is as the criterion.
Unless point out separately, all percentage ratios, umber, ratio etc. are all by weight.
When a quantity, concentration or other numerical value or parameter provide with scope, preferable range or a row preferred upper limit numerical value and preferred lower limit numerical value, it should be understood that open particularly any a pair of all scopes that constitute by any range limit or preferred value and any scope lower limit or preferred value, and no matter whether described scope is by open individually.Allly provide a certain numerical range part in this article, this scope all is intended to comprise its end points, and all integers and the mark that are positioned at this scope, unless point out separately.When scope of definition, do not wish scope of the present invention is defined in cited concrete numerical value.
" room temperature " is meant roughly envrionment temperature; For example about 20 to 25 ℃.
When term " about " was used for the end points of description value or scope, disclosure should be understood to include concrete value or related end points.
Measure word " one " or " a kind of " are used to describe element of the present invention or component.This only is for convenience and provides general sense of the present invention.This description should be understood to include one or at least one, and odd number also comprises plural number, anticipates unless clearly refer to him in addition.
Unless specifically indicate, the material of this paper, method and embodiment only are illustrative, are not to be intended to limit.
In general, the invention provides the method (especially by post-consumer polyester) of making polyester, described method is included in about room temperature to interior at least one temperature of about 300 ℃ of scopes, in the presence of catalyzer, makes post-consumer polyester contact at least a glycol.
In one embodiment, by at high temperature, in the presence of catalyzer, make post-consumer polyester contact at least a glycol generation transesterification reaction and make polyester by post-consumer polyester.In a specific embodiment, described method is by PET and 1, and the transesterification reaction of ammediol provides the Poly(Trimethylene Terephthalate) polymkeric substance by the post-consumer polyester that comprises polyethylene terephthalate (PET).In some preferred embodiments, 1, ammediol is biologically-derived 1, ammediol.
In some embodiments, post-consumer polyester comprises and is selected from following type of polymer: polyethylene terephthalate (2GT or PET or PETE), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT or 4GT), poly terephthalic acid pentadiol ester (5GT), poly terephthalic acid hexylene glycol ester (6GT), poly terephthalic acid heptanediol ester (7GT), polyether ester, their mixture, their blend and their multipolymer.Polyester polymeric species can comprise that PEN, 3GN and other contain naphthalenedicarboxylate copolymer.
In some embodiments, glycol is selected from C2-C20 alkanediol, polyalkylene glycol, alkoxyl group alkane glycol, alkenyloxy alkanediol, aklylene glycol, glycols, polyether glycol, phenoxy group alkanediol, alkyl phenoxy alkanediol, phenyl alkanediol, alkyl phenyl alkanediol and halogenated alkane glycol.In specific embodiments, glycol is selected from 1, ammediol, 1, the positive butyleneglycol of 3-, 2-methyl isophthalic acid, ammediol, neopentyl glycol (2), 1,4-butyleneglycol, triglycol and their mixture.
In a preferred embodiment, glycol is 1, ammediol.In some preferred embodiments, glycol is biologically-derived.In preferred embodiments, post-consumer polyester is derived from the beverage bottle that comprises polyethylene terephthalate, as carbonated drink or water bottle.In some preferred embodiments, 1, the mol ratio of ammediol and polyester about 5: 1 to about 1: 1 scope, and used catalyzer is an organic titanate.As used herein, " derived from beverage bottle " is meant by for example cut-out or grinds the processing beverage bottle so that they are used in the method for making polyester, and use the bottle of so processing that comprises post-consumer polyester to make polyester according to method of the present invention.
Use therein in some embodiments of biologically-derived glycol, method disclosed herein is preferably utilized than making polyester essential energy energy still less usually by the use polycondensation catalyst by the esterification of diprotic acid or diester and glycol.
In some embodiments, described method is included under about 200 ℃ of temperature to about 300 ℃ of scopes, in the presence of catalyzer, makes post-consumer polyester contact at least a glycol, and wherein said at least a glycol is biologically-derived 1, ammediol.In preferred embodiments, catalyst pack stanniferous or titanium.
In some embodiments, described method is included under about 200 ℃ of temperature to about 300 ℃ of scopes, in the presence of polymerizing catalyst, the post-consumer polyester that comprises polyethylene terephthalate with the glycol contact, wherein said at least a glycol is 1, and ammediol, wherein said polyester are 1 of at least 80 weight %, ammediol, and PET is maximum 20 weight %.Use for some, have in about 0.2 limiting viscosity to about 2.0 scopes according to the polyester of method manufacturing disclosed herein.
Can be used on such as in goods such as clothing fiber, carpet fiber, indoor decoration, moulded product, monofilament and wrapped product and the finished product according to the polyester of method manufacturing disclosed herein.
Be meant the polyester that the human consumer uses or the industrial utilization polyester produces afterwards with " post-consumer polyester ".Therefore, used, can be described as " industrial back polyester " so if " post-consumer polyester " once is used for industrial application rather than family expenses or other.Use post-consumer polyester as raw material.
The post-consumer polyester of example comprises polyethylene terephthalate (2GT or PET or PETE), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT or 4GT), poly terephthalic acid pentadiol ester (5GT), poly terephthalic acid hexylene glycol ester (6GT), poly terephthalic acid heptanediol ester (7GT) and polyether ester, as
The polyester elastomer polymkeric substance.The preferred post-consumer polyester that can be used for method disclosed herein comprises by the polyethylene terephthalate that reclaims code 1 sign.Yet post-consumer polyester also can be taked the form with the blend of one or more other polymeric materials.The polyester raw material that can be used for existing in the post-consumer polyester of method disclosed herein for example can comprise the thermoplastic elastomer based on polyester.
For example, can use " waste polyester plastic ".The suitable waste polyester plastic that can be used for method disclosed herein comprises the recyclable product that contains polyester components, as bottle, cup, container, packing, carpet, yarn fabric, fiber waste-material, film, engineering component, the molded and goods extruded, layered product, coating, tackiness agent etc.Preferred post-consumer polyester is derived from beverage bottle, as pop bottle or water bottle.
As used herein, " polyester " comprises by dihydroxy compound and polyacid condensation reaction (polyreaction or oligomerization) and the polymkeric substance and the oligopolymer kind that produce.Suitable polyhydric acid is a dihydric acid.The organic dihydric acid that preferably has formula HOOCACOOH, wherein A is alkylidene group, arylidene, alkenylene or two or more the combination in them.Each group of each A has about 2 to about 30, and preferred about 3 to about 25, more preferably from about 4 to about 20, and 4 to 15 carbon atoms most preferably from about.Suitable organic acid example includes but not limited to terephthalic acid, m-phthalic acid, phthalic acid, 4,4 '-the diphenylene dicarboxylic acid, succsinic acid, hexanodioic acid, pentanedioic acid, biphenyl dicarboxylic acid, naphthalic acid, two (to carbonyl phenyl) methane, 1, the 5-naphthalene dicarboxylic acids, 2, the 6-naphthalene dicarboxylic acids, 2, the 7-naphthalene dicarboxylic acids, 4,4 '-sulfonyldibenzoic acid, to (hydroxyl-oxethyl) phenylformic acid, succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, 1, the 12-dodecanedioic acid, and their derivative, as the dimethyl of these dicarboxylic acid, diethyl or dipropyl, and two or more the combination in them.
Aliphatic series or aromatic diacid or diester can be aliphatic series (comprising cyclic aliphatic) or aromatics or their combination, and preferably are selected from aromatic dicarboxylic acid and ester (preferred short-chain alkyl ester, and more preferably methyl ester) and their combination.Preferably aliphatic series or aromatic diacid, and most preferably aromatic dicarboxylic acid and their combination.Preferably, aliphatic series or aromatic diacid are the aromatic diacid that is selected from terephthalic acid, m-phthalic acid, and wherein terephthalic acid and m-phthalic acid and their mixture are preferred, and wherein terephthalic acid is most preferred.
The post-consumer polyester raw material that can be used for method disclosed herein can be made by other aromatic dicarboxylic acid or diester described in US6562457, US6599625 and the US7144972.
As indicated above, the post-consumer polyester that can be used for method disclosed herein comprises and also comprises the waste material of thermoplastic elastomer (TPE) as segmented copolyesters.Thermoplastic elastomer is a class combines the character of other two base polymer (thermoplastics that can reform and class rubber polymer elastomerics) after heating a polymkeric substance.A kind of form of TPE is a segmented copolymer, comprises polymer property usually and is similar to some blocks of thermoplastics character and some blocks that character is similar to elastomeric properties usually usually.Those blocks that character is similar to thermoplastics often are called as " firmly " fragment, often are called as " soft " fragment and character is similar to elastomeric those blocks.
Preferred polyester is those that are produced by the esterification of dimethyl terephthalate (DMT), terephthalic acid or m-phthalic acid and glycol.Polyester also comprises the copolyesters of the diol component in the repeating unit of the acid constituents of the repeating unit with at least a type and/or at least a type.
In the method for the invention, handle post-consumer polyester so that transesterification reaction to take place with one or more glycol.Suitable glycol comprises C2-C20 alkanediol, alkoxy C 2-C20 alkanediol, alkenyloxy C2-C20 alkanediol, C2-C20 aklylene glycol, phenoxy group C2-C20 alkanediol, alkyl phenoxy C2-C20 alkanediol, phenyl C2-C20 alkanediol, alkyl phenyl C2-C20 alkanediol and halo C2-C20 alkanediol.Preferred glycol comprises the C2-C20 alkanediol of straight or branched, for example ethylene glycol, Diethylene Glycol, two, three or TEG, two, three or four propylene glycol and two, three or four butyleneglycols, 1, the 2-propylene glycol, Isopropanediol, the 1-methyl propanediol, 1, ammediol, 1, the positive butyleneglycol of 3-, the 2-methyl isophthalic acid, ammediol, neopentyl glycol (2), the 2-methyl isophthalic acid, ammediol, 2,2-diethyl-1, ammediol, 2-ethyl-2-(methylol)-1, ammediol, 1, the 4-butyleneglycol, triethylene glycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1,2-, 1,3-, and 1,4 cyclohexane dimethanol, 1, the 7-heptanediol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, decamethylene-glycol, 1, the 12-dodecanediol, 3,3,4,4,5,5-hexafluoro-1, the 5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexylene glycol and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-ten hexafluoros-1,12-dodecanediol.Also cycloaliphatic diol preferably, for example 1,4-cyclohexanediol, 1,4 cyclohexane dimethanol and Isosorbide.A kind of especially preferred glycol is 1, ammediol (PDO).More specifically preferably biologically-derived (" biologically-derived ") 1, ammediol.
With 1, ammediol (PDO) is meant and comprises 1, ammediol, 1, ammediol dimer and 1, at least a or their reactant of mixture in the ammediol tripolymer.Used 1 in the method for the present invention, the ammediol reactant can by in the number of chemical approach any or obtain by the biochemical conversion approach.Preferred approach is described in US5015789, US5276201, US5284979, US5334778, US5364984, US5364987, US5633362, US5686276, US5821092, US5962745, US6140543, US6232511, US6235948, US6277289, US6284930, US6297408, US6331264, US6342646, US2004/0225161A1, US2004/0260125A1, US2005/0069997A1.Preferably, will have by weight purity as reactant or as the PDO of reactant composition, as being determined by gas chromatographic analysis greater than about 99%.
Although the dimer of PDO and PDO or in the tripolymer any can be used as the glycol in the described method, preferred reactant comprises about by weight 90% or more PDO.More preferably, reactant will comprise by weight 99% or more PDO.
A kind of preferred PDO is biologically-derived PDO.Biologically-derived PDO is through bio-chemical pathway synthetic PDO.The bio-chemical pathway of PDO once was described to utilize the feed of being produced by biological and renewable resources such as corn feed.For example, can be 1 with transformation of glycerol, the bacterial isolates of ammediol for example be present in bacterial classification klebsiella (Klebsiella), Citrobacter (Citrobacter), fusobacterium (Clostridium) and the lactobacillus (Lactobacillus).This technology is disclosed in several patents, comprises US5633362, US5686276 and US5821092, and these patents are all incorporated this paper into way of reference.In people's such as Nagarajan US5821092, a kind of use recombinant organisms is disclosed especially by glycerine biological production 1, the method for ammediol.This method has been introduced and has been used 1, the intestinal bacteria of the allos pdu dioldehydrase gene transformation that the 2-propylene glycol is special.The intestinal bacteria that transformed grow in the presence of as the glycerine of carbon source, and isolate 1 from growth medium, ammediol.Because bacterium and yeast can both be converted into glycerine with glucose (as primverose) or other carbohydrate, so method of the present invention provide a kind of can be used for producing polyester, polyethers and other polymkeric substance fast, cheapness and environmental protection 1, ammediol monomer source.
When 1, when ammediol is the glycol of using in the method for the invention, it also can comprise on a small quantity, preferably be no more than about 30% by weight, raw material more preferably no more than about 10% or remove reactant 1, comonomer diol outside the ammediol or its dimer or tripolymer, and can not reduce the effect of this method.The example of preferred comonomer diol comprises ethylene glycol, 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1, ammediol and C6-C12 glycol, as 2,2-diethyl-1, ammediol, 2-ethyl-2-methylol-1, ammediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexane diol and 1,4 cyclohexane dimethanol.A kind of preferred comonomer diol is an ethylene glycol.
In a preferred embodiment, method of the present invention under nitrogen atmosphere, in the presence of catalyzer, makes these type of plastics and 1 by under about 200 ℃ of temperature to about 300 ℃ of scopes, and ammediol reacts and transforms the post-consumer polyester plastics.Organic titanate as
The TPT titanium isopropylate can be used as the catalyzer of this method.The gained multipolymer comprises the Poly(Trimethylene Terephthalate) polymkeric substance of higher relatively part (for example surpass 50%) and the smaller portions repeating unit based on 2GT.In some embodiments, the amount of Poly(Trimethylene Terephthalate) is 70% or higher, even 95% or higher.
In another preferred embodiment; method of the present invention is by under about 200 ℃ of temperature to about 300 ℃ of scopes, under nitrogen atmosphere, in the presence of catalyzer; make this kind polyester and 1, ammediol reacts the post-consumer polyester (waste material) that transforms based on PET.Organic titanate as
TPT titanium isopropylate useful as catalysts.Resulting polymers is the copolyesters that comprises oxyethyl group and butoxy repeat units.As used herein, term " at least a glycol " is meant and uses at least two kinds of different glycol in some embodiments.
Use catalyzer to implement method of the present invention.In preferred embodiments, catalyst pack stanniferous and/or titanium.Can use can be as any sn-containing compound of esterifying catalyst.In general, catalyzer can be inorganic tin compound or organo-tin compound.The example of suitable tin compound includes but not limited to n-butylstannoic acid, octyl group stannic acid, dimethyl tin oxide, Dibutyltin oxide, dioctyl tin oxide, diphenyl tin oxide, three normal-butyl tin acetates, three normal-butyl chlorination tin, tri-n-butyl tin fluoride, ethyl tin monochloride, triethyl Tin tetrabromide, triethylacetic acid tin, trimethylammonium stannic hydroxide, fentin chloride, triphenyl Tin tetrabromide, fentin acetate or two or more combination in them.Tin oxide catalysts is preferred.These tin compounds generally are commercially available acquisitions.For example, n-butylstannoic acid can derive from Witco Chemical Corp., Greenwich, Conn..
Preferred titanium compound is an organic titanic compound.Also can use titanium dioxide.Four titan-alkoxide acid esters, this paper is also referred to as tetraalkyl titanate, is present most preferred organic titanic compound, because they are easy to get and effectively.The example of suitable four titan-alkoxide ester compounds comprises those that represented by general formula Ti (OR) 4, wherein each R is independently selected from each base and comprises 1 to about 30, preferred 2 to about 18, and most preferably alkyl or aryl and each R of 2 to 12 carbon atoms can be identical or different.Wherein to comprise 2 four titan-alkoxide acid esters to about 12 carbon atoms be most preferred to each straight or branched alkyl of hydrogen carboxyl, because they are relatively inexpensive, more be easy to get and effectively form solution.Four suitable titan-alkoxide acid esters include but not limited to purity titanium tetraethoxide, four titanium propanolates, tetraisopropoxy titanium, four titanium n-butoxide, four hexyloxy titaniums, four 2-ethyl hexyl oxy titaniums, four octyloxy titaniums and two or more combination in them.
Four suitable titan-alkoxide acid esters can be produced to form four titan-alkoxide acid esters or tetraalkyl titanate with alcohol by for example mix titanium tetrachloride in the presence of alkali such as ammonia.Described alcohol can be ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.Can then from reaction mixture, distill out the four titan-alkoxide acid esters that four titan-alkoxide acid esters are regained production like this by at first removing by-product ammonium chloride through any way known to those skilled in the art such as filtration.This method can be carried out under about 0 temperature to about 150 ℃ of scopes.Those of R base that also can be by having maximum C4 and each molecule have the transesterification reaction of the alcohol that surpasses 4 carbon atoms and produce the titanic acid ester with longer alkyl.The example of the organic titanic compound of commercially available acquisition includes but not limited to
The TPT titanium isopropylate and
The TBT tetra-n-butyl titanate derives from E.I.du Pont de Nemours and Company, Wilmington, Del., U.S.A..
If use had both comprised tin and also wrapped titaniferous catalyzer, the weight ratio of tin compound and titanium compound can be any ratio so, but if this ratio catalysis acid and 1, the esterification of ammediol.In general, this ratio can be about 0.01: 1 to about 100: 1, and preferred about 0.1: 1 to about 10: 1.
Can produce catalyzer by any method known to those skilled in the art.For example, can be by in esterification medium, making up tin compound or titanium compound and acid or 1 respectively, ammediol is produced catalyzer.Also can be by combination tin compound or titanium compound and acid, 1, ammediol or both are the produce in situ catalyzer in esterification medium.Preferably, by producing with combination tin compound or titanium compound before esterification medium contacts.In other words, the tin compound of producing before the catalyzer of premix preferably is contained in and contacts with esterification medium and titanium compound, basically by or by forming with the tin compound and the titanium compound of production before esterification medium contact.More preferably, before being used for described method at organic solvent mixing tin and titanium catalyst.Can use any solvent of dissolving basically or dispersed catalyst and nonintervention polyreaction.For convenience, organic solvent can be 1, ammediol.Preferably, the amount that tin exists between about 2 and 400ppm between, and the amount that exists of titanium between about 2 and 400ppm between, each fundamental quantity is based on the weight of reactant in the esterification medium.
Method of the present invention also permits controlling by the initial molar ratio of polyester in control alkanediol and the post-consumer polyester ratio of sour repeating unit and alkoxyl group repeating unit.In a preferred embodiment, in alkanediol and the post-consumer polyester mol ratio of polyester at about 100: 1 to about 1: 1 scope.In alkanediol and the post-consumer polyester the more preferably mol ratio of polyester at 5: 1 to about 1: 1 scope.
The transesterification reaction of described method can take place to about 300 ℃ preferred range at about 200 ℃.In one embodiment, temperature can be remained on a bit for entire reaction.In another embodiment, temperature is remained on similar and different for some time of more than one temperature spot once or surpass once.
Can conventional additives be mixed in the polyester product of this method by during esterification, adding.Suitable additive comprises matting agent (for example TiO2, zinc sulphide or zinc oxide), tinting material (for example dyestuff), stablizer (for example antioxidant, uvioresistant photo etching, thermo-stabilizer etc.), weighting agent, fire retardant, pigment, biocide, static inhibitor, white dyes, filler, processing aid, tackifier and other functional additive.
The esterification that the polyester of making by method of the present invention generally can be used on wherein by diprotic acid or diester and glycol obtains in any application of polyester.For example, polyester can be used to make fiber and uses to be used for all fibres, use as clothes, fabric, carpet, rope, tyre assembly, weaving material, nonwoven material, wrapping material, engineering, as moulding part, extrude parts, laminate member, lagging material, electrically insulating material, trolley part, outside and inside, bottle, beverage bottle and other container.Polyester also can be used for making film, comprises injection molded article, injection drawing blow goods and other moulded products.For example, polyester (for example can be used to make continuous fibre, be used in the yarn fabric end-use as the fabric that is used for clothes and be used in carpet fiber, comprise in varicosity continuous filament yarn (BCF) fiber those) and staple fibre (as be used in the yarn fabric end-use, comprise in fabric, carpet fiber, indoor decoration fiber and the automobile fiber end-use that is used in the clothes those.)
Embodiment
Embodiment 1-is poly-to propylene glycol dibenzoate by the PET preparation
Polymkeric substance
The 60g PET-3934 that packs in the three-necked flask of a 250mL (derives from E.I.du Pontde Nemour s﹠amp; Co., Wilmington DE) (derives from E.I.du Pont de Nemours﹠amp with the biologically-derived PDO of 38g; Co., Wilmington, DE), the mol ratio that makes PDO and pet polymer is 1.6: 1.In polymerization reaction mixture, add
TPT titanium isopropylate (36mg) is as catalyzer.
Reaction mixture is under the nitrogen environment, temperature is increased to 230 ℃ gradually.With temperature remain on 230 ℃ about 1 hour.Further temperature is increased to 250 ℃, and under the vacuum of 0.2mm (2.66X10-5MPa), kept 1.5 hours at 250 ℃.When reaction finishes, make flask cooling and collected polymer.
Resulting polymers has the limiting viscosity (IV) of 209 ℃ fusing point and 0.85dL/g.The IV of polymkeric substance is the limiting viscosity of polymkeric substance, and is defined as the reduced viscosity of polymkeric substance in the infinite dilution solution or the ultimate value of limiting viscosity.Detect through NMR, poly-weight ratio to propylene glycol dibenzoate and PET is 85: 15.
Embodiment 2-is poly-to propylene glycol dibenzoate by the PET preparation
Polymkeric substance
The biologically-derived PDO of 60g PET-3934 and 71g that packs in the three-necked flask of a 250mL, the mol ratio that makes PDO and pet polymer is about 3: 1.In polymerization reaction mixture, add
TPT titanium isopropylate (36mg) is as catalyzer.Reaction mixture is under the nitrogen environment, temperature is increased to 220 ℃ gradually.With temperature remain on 230 ℃ about 1 hour.Further temperature is increased to 250 ℃, and under the vacuum of 0.2mm (2.66X10-5MPa), kept 1.5 hours at 250 ℃.When reaction finishes, make flask cooling and collected polymer.
Resulting polymers has 220.5 ℃ fusing point and the IV of 0.81dL/g.Detect through NMR, poly-weight ratio to propylene glycol dibenzoate and PET is 93: 7.
Embodiment 3-is prepared by PBT
Multipolymer
The 65g PBT that packs in the three-necked flask of a 250mL (derives from E.I.du Pont deNemours﹠amp; Co., Wilmington is DE) with the biologically-derived PDO (mol ratio that makes PDO and PBT polymkeric substance is about 3: 1) of 76g.In polymerization reaction mixture, add
TPT titanium isopropylate (36mg) is as catalyzer.Reaction mixture is under the nitrogen environment, temperature is increased to 220 ℃ gradually.With temperature remain on 220 ℃ about 1 hour.
Further temperature is increased to 250 ℃, and under the vacuum of 0.2mm (2.66X10-5MPa), kept 1 hour at 250 ℃.When reaction finishes, make flask cooling and collected polymer.
Resulting polymers has 195 ℃ fusing point and the IV of 0.88dL/g.Detect through NMR, poly-weight ratio to propylene glycol dibenzoate and PBT is 72: 28.
Embodiment 4-is made poly-to propylene glycol dibenzoate by PET
Polymkeric substance
Pack in one 25 gallons autoclave 100lbs PET-3934 and the biologically-derived PDO of 80lbs, the mol ratio that makes PDO and pet polymer is about 2: 1.In polymerization reaction mixture, add
TPT titanium isopropylate (17g) is as catalyzer.Reaction mixture is under the nitrogen environment, temperature is increased to 230 ℃ gradually.With temperature remain on 230 ℃ about 1 hour.Further temperature is increased to 250 ℃, and under the vacuum of 0.2mm (2.66X10-5MPa), kept 4 hours at 250 ℃.When reaction finishes, with the polymkeric substance granulation.
Resulting polymers has 214.8 ℃ fusing point and the IV of 0.76dL/g.Detect through NMR, poly-weight ratio to propylene glycol dibenzoate and PET is 90: 10.
Embodiment 5-is made poly-to propylene glycol dibenzoate by PET
Polymkeric substance
Pack in one 25 gallons autoclave 100lbs PET-3934 and the biologically-derived PDO of 118lbs, the mol ratio that makes PDO and pet polymer is about 3: 1.In polymerization reaction mixture, add
TPT titanium isopropylate (18g) is as catalyzer.Reaction mixture is under the nitrogen environment, temperature is increased to 230 ℃ gradually.With temperature remain on 230 ℃ about 1 hour.Further temperature is increased to 250 ℃, and under the vacuum of 0.2mm (2.66X10-5MPa), kept 4.5 hours at 250 ℃.When reaction finishes, with the polymkeric substance granulation.
Resulting polymers has 219 ℃ fusing point and the IV of 0.82dL/g.Detect through NMR, poly-weight ratio to propylene glycol dibenzoate and PET is 95: 5.
Claims (21)
1. method that is used for being made by post-consumer polyester polyester, described method are included under the temperature of about room temperature to about 300 ℃ of scopes, in the presence of polymerizing catalyst, described post-consumer polyester are contacted with at least a glycol.
2. the process of claim 1 wherein that described catalyzer is selected from tin catalyst, antimony catalyst, germanium catalyst and titanium catalyst.
3. the process of claim 1 wherein that described catalyzer is selected from tin catalyst and titanium catalyst.
4. the process of claim 1 wherein that described post-consumer polyester is derived from the polyester article of being made by the polyester with recovery code 1.
5. the process of claim 1 wherein that described post-consumer polyester comprises is selected from following type of polymer: poly-to ethylene glycol dibenzoate, poly-to propylene glycol dibenzoate, poly-to dibenzoic acid butanediol ester, poly-to dibenzoic acid pentadiol ester, poly-to dibenzoic acid hexylene glycol ester, poly-to dibenzoic acid heptanediol ester, polyether ester, their mixture, their blend and their multipolymer.
6. the process of claim 1 wherein that described at least a glycol is selected from C2-C20 alkanediol, polyalkylene glycol, alkoxyl group alkane glycol, alkenyloxy alkanediol, aklylene glycol, glycols, polyether glycol, phenoxy group alkanediol, alkyl phenoxy alkanediol, phenyl alkanediol, alkyl phenyl alkanediol and halogenated alkane glycol.
7. the method for claim 6, wherein said at least a glycol is selected from 1, ammediol, 1, the positive butyleneglycol of 3-, 2-methyl isophthalic acid, ammediol, neopentyl glycol (2), 1,4-butyleneglycol, triglycol and their mixture.
8. the process of claim 1 wherein describedly 1, ammediol is biologically-derived.
9. the process of claim 1 wherein that described polyester comprises polyethylene terephthalate.
10. the process of claim 1 wherein the mol ratio of polyester in described at least a glycol and the described post-consumer polyester at about 100: 1 to about 1: 1 scope.
11. the method for claim 10, the mol ratio of wherein said glycol and described polyester at about 5: 1 to about 1: 1 scope.
12. the method for claim 10, wherein said catalyzer is an organic titanate.
13. method that is used for making polyester by post-consumer polyester, described method is included under about 160 ℃ of temperature to about 300 ℃ of scopes, in the presence of the catalyzer that comprises tin or titanium, described post-consumer polyester is contacted with at least a glycol, and wherein said at least a glycol is biologically-derived glycol.
14. polyester by the preparation of the method for claim 1.
15. by the polyester of the method for claim 14 preparation, wherein said polyester is at least 80 weight %
Poly-to propylene glycol dibenzoate, and PET is maximum 20 weight %.
16. the finished product of making by the polyester of claim 14.
17. comprise the fiber of the polyester of claim 14.
18. comprise the moulded product of the polyester of claim 14.
19. comprise the wrapped product of the polyester of claim 14.
20. the polyester of claim 14, described polyester have about 0.2 to about 2.0 limiting viscosity.
21. the process of claim 1 wherein that described catalyzer is a titanium dioxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US88207206P | 2006-12-27 | 2006-12-27 | |
| US60/882,072 | 2006-12-27 | ||
| US11/866,076 | 2007-10-02 |
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| Publication Number | Publication Date |
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| CN101568568A true CN101568568A (en) | 2009-10-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800481279A Pending CN101568568A (en) | 2006-12-27 | 2007-12-20 | Processes for manufacturing polyesters from post-consumer polyester |
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| CN (1) | CN101568568A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102656619A (en) * | 2009-12-14 | 2012-09-05 | 艾利丹尼森公司 | Label and method of manufacturing the same with recycled material |
| CN103436990A (en) * | 2013-08-16 | 2013-12-11 | 盛虹集团有限公司 | Recycled polyester sea-island fiber and preparation method thereof |
| TWI828914B (en) * | 2019-10-01 | 2024-01-11 | 南韓商Ｓｋ化學公司 | Polyester resin blend and article formed from the same |
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2007
- 2007-12-20 CN CNA2007800481279A patent/CN101568568A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102656619A (en) * | 2009-12-14 | 2012-09-05 | 艾利丹尼森公司 | Label and method of manufacturing the same with recycled material |
| CN107447326A (en) * | 2009-12-14 | 2017-12-08 | 艾利丹尼森公司 | Label and the method from salvage material manufacture label |
| US9940853B2 (en) | 2009-12-14 | 2018-04-10 | Avery Dennison Retail Information Services, Llc | Label and method of manufacturing the same from recycled material |
| CN103436990A (en) * | 2013-08-16 | 2013-12-11 | 盛虹集团有限公司 | Recycled polyester sea-island fiber and preparation method thereof |
| CN103436990B (en) * | 2013-08-16 | 2015-08-05 | 盛虹集团有限公司 | A kind of recycled polyester islands-in-sea type fibre and preparation method thereof |
| TWI828914B (en) * | 2019-10-01 | 2024-01-11 | 南韓商Ｓｋ化學公司 | Polyester resin blend and article formed from the same |
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Open date: 20091028 |