CN103897157B - The method of aliphatic polyester is prepared by glycol - Google Patents

The method of aliphatic polyester is prepared by glycol Download PDF

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Publication number
CN103897157B
CN103897157B CN201210572950.2A CN201210572950A CN103897157B CN 103897157 B CN103897157 B CN 103897157B CN 201210572950 A CN201210572950 A CN 201210572950A CN 103897157 B CN103897157 B CN 103897157B
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glycol
formula
polyester
integer
solvent
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CN103897157A (en
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谢琼丹
唐甜
左刚
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to CN201210572950.2A priority Critical patent/CN103897157B/en
Priority to PCT/US2013/076863 priority patent/WO2014105685A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a kind of method preparing aliphatic polyester, described method is by by glycol, and the mixture of ruthenium catalyst and the optional solvent that exists or solvent systems heats.According to method of the present invention, described method, under the temperature range of 100 ° of C to 300 ° of C, heats 1-60 hour and obtains described aliphatic polyester with high yield.

Description

The method of aliphatic polyester is prepared by glycol
Technical field
The present invention relates to the method directly being prepared aliphatic polyester under the existence of ruthenium catalyst by glycol.
Background technology
Polyester is formed by diacid and glycol polycondensation usually.The synthesis of commercialization polyester is usually directed to two steps: (1) condensation/transesterify: diacid or its ester and excessive glycol are carried out at relatively low temperature reacting to form oligopolymer, remove volatile small molecules continuously simultaneously, such as, water, ethanol or methyl alcohol; (2) be polymerized: oligopolymer is heated under certain high temperature (polymerization of such as PET carries out under 250 ° of C) and remove more volatile excess monomer under negative pressure, be often glycol, thus obtain the polyester of high molecular.The main drawback of condensation polymerization method needs to remove unnecessary monomer under a high vacuum with under high temperature, this degraded that can increase cost of energy and cause polyester product possible.
In addition, polyester also can be prepared by the ring-opening polymerization of cyclic lactone.Such as, namely polycaprolactone is by ring-opening polymerization caprolactone, and it is a kind of cyclic ester monomer, commercially produces.The multipolymer of ester also by the mixing of cyclic lactone monomer is carried out ring-opening polymerization to prepare, can be shown in that N.Nomuraetal is at JACS2010, disclosed in 132,1750-1751.
Recently, the people such as Milstein, at Science2007,317, to disclose in 790 by using Ru(ruthenium) catalyzer can synthesize various ester from various alcohol and release hydrogen is its unique by product.This catalytic dehydrogenation esterification process provides a lot of advantage, as high yield and high conversion and minimum by product, so be also eco-friendly.
Based on monomer used, polyester can be divided into three classes, comprises aliphatic polyester, semi-aromatic polyester and aromatic polyester.When describing polyester, described polyester is normally described based on monomer used.Such as, PGA or polyglycolic acid (PGA) are aliphatic polyesters, and it is prepared by the condensation of oxyacetic acid; And polyethylene terephthalate (PET) is semi-aromatic polyester, it is the polycondensation preparation by terephthalic acid and ethylene glycol.
Consider the biodegradable characteristic of aliphatic polyester as PGA, this kind polyester is just receiving more concern recently.Therefore, any improvement obtained in its production technique is all welcome.Applicant of the present invention finds, aliphatic polyester can be prepared from various glycol by similar dehydrogenation polymerization method.Described polymerization can be carried out in the presence of the solvent, or can carry out under condition of no solvent.
Summary of the invention
The invention provides a kind of method of the polyester for the preparation of formula 1,
Described method comprises:
The glycol of (a) hybrid 2, the ruthenium catalyst of formula 3
With solvent or the solvent systems of optional existence, with forming reactions mixture; And
B described reaction mixture, under temperature is the scope of 100-300 DEG C, is heated 1-60 hour to form the polyester of formula 1 by ();
Wherein:
A is-(CH 2) p-W q-(CH 2) r-, wherein W is selected from C 3-C 10cycloalkyl, p is the integer of 1 to 8, q be 0 or 1, r be 1 to 8 integer, and when q is 0, the summation of p and r is the integer of 3 to 14;
The summation of k and n is the integer of 10 to 150;
L 1and L 2be selected from P (R independently of one another 1) 2, P (OR 2) 2with N (R 3) 2group;
L 3be selected from CO, P (R 1) 3, P (OR 2) 3, NO +, nitrile (R 4and isonitrile ((R CN) 5nC) bielectron list coordinating donor; And
R 1, R 2, R 3, R 4and R 5it is the group being selected from alkyl, cycloalkyl, aryl, alkylaryl, heterocyclic radical and heteroaryl independently of one another.
Hereinafter method of the present invention will be described in further detail.In following scheme, except as otherwise noted, each definition as above limited.
Embodiment
All publications mentioned in this article, patent application, patent and other reference, if do not illustrated on the contrary, all quote its full content clearly and add herein, as them in this article by full disclosure.
Unless otherwise defined, all technology used herein and scientific terminology have the identical implication usually understood with one skilled in the art of the present invention.When there is contradiction, be as the criterion with the definition in this specification sheets.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " comprising ", " having ", " containing " or its other distortion any, be intended to cover the comprising of non-exclusionism.Such as, comprise the composition of listed elements, step, method, goods or device and need not be only limitted to those key elements, but other key element of clearly not listing or the intrinsic key element of this kind of composition, step, method, goods or device can be comprised.
Conjunction " by ... composition " get rid of any key element, step or the component do not pointed out.If in claim, this phrase will make claim be closed, make it not comprise material except those materials described, but except relative customary impurities.When phrase " by ... composition " to appear in the clause of claim main body instead of immediately preceding after theme time, it is only limited to the key element described in this clause; Other key element is not excluded outside described claim as a whole.
Conjunction " substantially by ... composition " for limiting composition, method or device; it comprises material, step, feature, component or key element except those words are discussed, and prerequisite is that these additional material, step, feature, component or key elements can not the characteristics of basic and novelty of the claimed invention of materially affect.Term " substantially by ... composition " rank, position between " comprising " and " by ... form " between.
Term " comprise " be intended to comprise by term " substantially by ... composition " and " by ... form " embodiment that comprises.Similarly, term " substantially by ... composition " is intended to comprise the embodiment comprised by term " by ... composition ".
In the foregoing description, in substituting group, the sum of carbon atom is represented by prefix " Ci-Cj ", and wherein i and j is the numerical value of 1 to 16.
In one embodiment, term " alkyl ", when being used alone or as another group a part of, refers to " C 1to C 16alkyl ", and refer to linear in cladodification, saturated or unsaturated (such as thiazolinyl, alkynyl) group, unsaturated group is only applicable to the situation when the carbonatoms in alkyl is more than or equal to 2, and can comprise mixed structure.Preferred alkyl comprises 1 to 12 carbon atom (C 1to C 12alkyl).Preferred alkyl comprises 1 to 10 carbon atom (C 1to C 10alkyl).The example of saturated alkyl includes but not limited to, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, tert-pentyl and hexyl.The example of thiazolinyl includes but not limited to, vinyl, allyl group, butenyl etc.The example of alkynyl includes but not limited to, ethynyl, proyl etc.Similarly, term " C 1to C 12alkylidene group " refer to the divalent group of 1 to 12 carbon.
Alkyl can be unsubstituted, or replaced by one or more substituting group, described substituting group is selected from halogen, hydroxyl, alkoxyl group, aryloxy, alkyl-aryloxy, heteroaryloxy, oxo, cycloalkyl, phenyl, heteroaryl, heterocyclic radical, naphthyl, amino, alkylamino, arylamino, heteroaryl amino, dialkyl amido, ammonia diaryl base, alkane virtue is amino, the assorted virtue of alkyl is amino, the assorted virtue of aryl is amino, acyl group, acyloxy, nitro, carboxyl, formamyl, amide group, cyano group, alkylsulfonyl, sulfonamido, sulfinyl, sulfonamido, thiol group, alkylthio, arylthio or alkyl sulphonyl.Any substituting group can be unsubstituted, or is replaced by above-mentioned arbitrary substituting group further.As an example, " alkoxyalkyl " is the alkyl that alkoxy replaces.
Herein term " cycloalkyl " be used alone or as another group a part of time, refer to " C 3to C 10cycloalkyl " and refer to saturated or undersaturated (such as cycloalkenyl group, cycloalkynyl radical) monocycle or polycyclic moiety.The limiting examples of cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, two rings [2.2.1] heptyl, two rings [2.2.2] octyl group or adamantyl.The example of cycloalkenyl group comprises cyclopentenyl, cyclohexenyl etc.Cycloalkyl can be unsubstituted, or is replaced by one or more substituting group, described substituting group as the above-mentioned substituting group to alkyl define.Similarly, term " cycloalkylidene " refers to divalent cycloalkyl, and as defined above, wherein cycloalkyl is connected with two other groups difference bondings on two positions.
Herein term " aryl " be used alone or as another group a part of time, refer to the aromatic ring system containing 6-14 ring carbons.Aryl rings can be monocycle, dicyclo, three rings etc.The limiting examples of aryl is phenyl, naphthyl comprises 1-naphthyl and 2-naphthyl etc.Aryl can be unsubstituted or by the carbon atom that can be substituted by one or more as above-mentioned to alkyl the group that limits replace.Aralkyl represents the aryl (such as benzyl) being bonded to alkyl.
Herein term " heteroaryl " be used alone or as another group a part of time, represent that comprising at least one annular atoms is heteroatomic heteroaromatic system, described heteroatoms is selected from nitrogen, sulphur and oxygen.Heteroaryl comprises 5 or more ring member nitrogen atoms.Heteroaryl can be monocycle, dicyclo, three rings etc.Heteroaryl also comprises benzheterocycle.If nitrogen is ring member nitrogen atoms, the present invention also comprises the heteroaryl of nitrogenous N-oxide compound.The limiting examples of heteroaryl comprises thiophene, thionaphthene, 1-aphthothiophenes, thianthrenyl, furyl, benzofuryl, pyrryl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, indyl, pseudoindoyl, indazolyl, purine radicals, isoquinolyl, quinolyl, naphthyridinyl, quinoxalinyl, quinazolyl, cinnolines base, pteridine radicals (pteridinyl), carbolinyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl etc.Heteroaryl can be unsubstituted or by the atom that can be substituted by one or more as above-mentioned to alkyl the group that limits replace.
When herein term " heterocycle " or " heterocyclic radical " is used alone or uses as the part of another group, represent to have 1 to 4 heteroatomic ternary to octatomic ring, described heteroatoms is as oxygen, sulphur and/or nitrogen.These ternarys to octatomic ring can be saturated, completely undersaturated or part is undersaturated.The limiting examples of heterocycle comprises Oxyranyle (oxiranyl), oxetanyl, piperidyl, pyrrolidyl, pyrrolinyl, pyrazolinyl, pyrazolidyl, morpholinyl, thio-morpholinyl, pyranyl, thiopyranyl, piperazinyl, indyl, dihydrofuran base, tetrahydrofuran base, dihydro-thiophene base, tetrahydro-thienyl, dihydro pyranyl, THP trtrahydropyranyl etc.Heterocyclic radical can be unsubstituted, or by available atom by one or more as above-mentioned to alkyl the group that limits replace.
Above the restriction of various group and preferable range are all applicable to the corresponding various group had described in this specification sheets and claim in the compound of formula 1, formula 2, formula 3 and formula 4.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is appreciated that all scopes specifically disclosing and formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, no matter and whether this scope separately discloses.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc.When numerical range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers within the scope of this and mark.
When term " about " is used to the end value describing numerical value or scope, describedly its concrete numerical value related to or end value openly should be understood to include.
In addition, unless there is clear and definite contrary instruction, otherwise "or" refers to the "or" of comprising property instead of the "or" of exclusiveness.Such as, the following any one form A "or" B:A that all satisfies condition is true (or existence) and B is pseudo-(or not existing), A is not for pseudo-(or existing) and B is true (or existence), and A and B is very (or existence).
In addition, the indefinite article " one " before key element of the present invention or component and " one " are to quantitative requirement (i.e. occurrence number) unrestriction of key element or component.Therefore " one " or " one " should be read as and comprise one or at least one, and the key element of singulative or component also comprise plural form, unless the obvious purport of described quantity refers to singulative.
" mol% " refers to molar percentage.
In specification sheets of the present invention and claims, term " homopolymer " refers to the polymkeric substance obtained by a kind of polymerization of repeating unit.Term " multipolymer " refers to the polymkeric substance comprising the copolymerization units obtained by two or more comonomer." copolymer " refers to the polymkeric substance be substantially made up of the unit being derived from two kinds of comonomers, and " terpolymer " refers to the multipolymer be substantially made up of the unit being derived from three kinds of comonomers.Such as, the polyester of formula 1 is made up of two repeating units, therefore can be considered to a kind of multipolymer or be total to binary polymers.
Embodiments of the present invention comprise:
Embodiment 1: the method describing the polyester of preparation formula 1 in summary of the invention, wherein L 1p (R 1) 2.
Embodiment 2: the method for embodiment 1, wherein R 1it is the tertiary butyl.
Embodiment 3: the method describing the polyester of preparation formula 1 in summary of the invention, wherein L 2n (R 3) 2.
Embodiment 4: the method for embodiment 3, wherein R 3it is ethyl.
Embodiment 5: the method describing the polyester of preparation formula 1 in summary of the invention, wherein L 3cO.
Embodiment 6: the method describing the polyester of preparation formula 1 in summary of the invention, the glycol of the described formula 2 of scope relative to every mole of the amount of the ruthenium catalyst of wherein said formula 3 is about 0.05 % by mole to about 5 % by mole.
Embodiment 7: the method for embodiment 6, the glycol of the described formula 2 of scope relative to every mole of the amount of the ruthenium catalyst of wherein said formula 3 is about 0.1 % by mole to about 1 % by mole.
Embodiment 8: the method for embodiment 7, the glycol of the described formula 2 of scope relative to every mole of the amount of the ruthenium catalyst of wherein said formula 3 is about 0.2 % by mole to about 0.8 % by mole.
Embodiment 9: the method describing the polyester of preparation formula 1 in summary of the invention, wherein said solvent or solvent system are selected from hexanaphthene, benzene, toluene, p-Xylol, m-xylene, o-Xylol, phenylmethylether, sym-trimethylbenzene, tetrahydrofuran (THF), 1,2-glycol dimethyl ether, Isosorbide-5-Nitrae-diox, diglyme, dimethyl formamide, methyl-sulphoxide and its mixture.
Embodiment 10: the method describing the polyester of preparation formula 1 in summary of the invention, the glycol of the described formula 2 of scope relative to every mole of the amount of wherein said solvent or solvent system is about 0.01L to about 0.45L.
Embodiment 11: the method for embodiment 10, the glycol of the described formula 2 of scope relative to every mole of the amount of wherein said solvent or solvent system is about 0.1L to about 0.4L.
Embodiment 12: the method describing the polyester of preparation formula 1 in summary of the invention, wherein the polyester of wherein said formula 1 is formed under inert gas atmosphere.
Embodiment 13: the method for embodiment 12, the polyester of wherein said formula 1 is formed under the pressure of about 1bar to about 10bar.
Embodiment 14: the method for embodiment 13, the polyester of wherein said formula 1 is formed under the pressure of about 1bar to about 5bar.
Embodiment 15: the method for embodiment 14, the polyester of wherein said formula 1 is formed under close to the pressure of normal atmosphere (An).
Embodiment 16: the method describing the polyester of preparation formula 1 in summary of the invention, wherein said heating carries out under the temperature range of about 120 ° of C to about 260 ° of C.
Embodiment 17: the method describing the polyester of preparation formula 1 in summary of the invention, the glycol of wherein said formula 2 is C 5-C 16alkyl diol, C 5-C 16cycloalkylalkyl glycol or its mixture.
Embodiment 18: the method for embodiment 17, the glycol of wherein said formula 2 is selected from 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, decamethylene-glycol, 1,12-dodecanediol, 1,14-tetradecane diols, 1,16-hexadecane diol, 1,3-CHDM, 1,4 cyclohexane dimethanol, 1,4-hexanaphthene di-alcohol, Isosorbide-5-Nitrae-hexanaphthene two propyl alcohol and its mixture.
Described by summary of the invention part, embodiments of the present invention comprise other embodiment any described herein, can combine by any way, and the description of variable in embodiment is not only for method of the present invention and for polyester prepared therefrom.
The present invention is by more detailed description hereinafter.
As shown in scheme 1, in the method for the invention, the polyester of formula 1 is prepared by the solvent that makes the glycol of formula 2 contact with the ruthenium catalyst of formula 3 and optionally to exist or solvent systems.
scheme 1
glycol
In the glycol method used in the present invention of multiple formula 2, comprise C 5-C 16alkyl diol is (when A is-(CH 2) p-W q-(CH 2) r-, q is 0, and p's and r and be 3 to 14 integer time); C 5-C 16cycloalkylalkyl glycol (when q is 1).
Suitable C 5-C 16the example of alkyl diol is 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane, 1,12-dodecanediol, 1,13-tridecane diols, 1,14-tetradecane diols, 1,15-pentadecane diols or 1,16-hexadecane diol.
C 5-C 16the example of cycloalkylalkyl glycol is 1, 2-cyclopropane dimethanol, 1, 2-cyclobutanedimethanol, 1, 3-pentamethylene dimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 3-(methylol) hexanaphthene ethanol, 1, 2-hexanaphthene di-alcohol, 1, 3-hexanaphthene di-alcohol, 1, 4-hexanaphthene di-alcohol, 1, 4-hexanaphthene two propyl alcohol, two rings [2.2.1] heptane-2, 3-dimethanol, two rings [2.2.2] octane-1, 4-dimethanol, two rings [2.2.2] octane-2, 3-dimethanol, or octahydro-4, 7-endo-methylene group-1H-indenes-1, 5-dimethanol (CAS28132-01-6) or 1, 3-diamantane dimethanol (CAS17071-62-4).
The mixture of above-mentioned glycol also may be used in the present invention.
Preferred glycol comprises 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecane diols, 1,16-hexadecane diol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Isosorbide-5-Nitrae-hexanaphthene di-alcohol, Isosorbide-5-Nitrae-hexanaphthene two propyl alcohol or its mixture.
In an embodiment of the invention, the glycol of formula 2 comprises 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, decamethylene-glycol, 1,12-dodecanediol, 1,14-tetradecane diols, 1,16-hexadecane diol, 1,3-CHDM, 1,4 cyclohexane dimethanol, 1,4-hexanaphthene di-alcohol, Isosorbide-5-Nitrae-hexanaphthene two propyl alcohol and its mixture.
ruthenium catalyst
Method of the present invention by the ruthenium of formula 3 (Ru) complex catalysis, without the need to alkali or acid cocatalyst.
In a preferred embodiment, Ru catalyzer is by the compounds represented of formula 3a:
Wherein each R 1and R 3all the groups independently selected from alkyl, cycloalkyl, aryl, alkylaryl, heterocyclic radical and heteroaryl.
In another embodiment, the compound of formula 3a, wherein R 1be the tertiary butyl and R 3be ethyl by formula 3b compounds represented, it is commercially available derives from StremChemicalInc..
It is understood that when catalyzer comprises one or more chiral centre, all steric isomers are also included within scope of the present invention.
Method of the present invention is carried out usually under the existence of ruthenium catalyst, and the amount of ruthenium catalyst is about 0.05 % by mole of-Yue 5 % by mole relative to the glycol of every mole of formula 2, or about 0.1 % by mole of-Yue 1 % by mole or about 0.2 % by mole-Yue 0.8 % by mole.
the solvent of reaction
Method of the present invention can be carried out under solvent or solvent systems existent condition.Described " solvent systems " is mean that this solvent systems is the mixture of more than one solvent in this article.Preferably, described solvent systems is homogeneous phase solution and is anhydrous.The limiting examples of suitable solvent comprises hexanaphthene, benzene, toluene, p-Xylol, m-xylene, o-Xylol, phenylmethylether, sym-trimethylbenzene, tetrahydrofuran (THF) (THF), 1,2-glycol dimethyl ether, Isosorbide-5-Nitrae-diox, diglyme, dimethyl formamide (DMF), methyl-sulphoxide (DMSO) or its mixture.
Method of the present invention also can be carried out in the absence of a solvent.Term " solvent-free " or " not containing solvent " are used interchangeably in this article; It means in the methods of the invention, described reaction mixture, based on the total weight of reaction mixture, containing the solvent being less than 0.1 % by weight, is preferably less than the solvent of 0.01 % by weight.
the mode of mixing
The method of scheme 1 normally by the mixture of the compound of formula 2 and the Ru catalyzer of formula 3, is carried out under solvent or the dispensable situation of solvent systems.
In order to processing ease, first the glycol of formula 2 is joined in reaction vessel.Usually at room temperature and rare gas element as under nitrogen or argon gas atmosphere, Ru catalyzer is joined in the reaction vessel of the glycol containing formula 2.If use solvent or solvent system, it finally just adds.
As shown in scheme 1, described method can produce hydrogen is by product.Usually at high temperature carry out owing to reacting, the hydrogen that great majority generate can disengage from reaction mixture.Described reaction is usually under standard pressure (about 1bar), and carry out under having stable inert gas flow, the hydrogen generated in reaction process can be blown away, to avoid the hydrogen accumulating high density in reaction vessel.
Temperature of reaction has no particular limits, and condition is its at least low than the boiling point of glycol 10 ° of C, to avoid the loss of reactant.If have solvent or solvent system to exist, then temperature of reaction can up to the reflux temperature of this reaction mixture.Described temperature of reaction, usually between about 100 ° of C to about 300 ° of C, is preferably between about 120 ° of C to about 260 ° of C.
The temperature of reaction depending on batch sizes and use, those skilled in the art can determine to react the time of carrying out aptly.
The product of formula 1 can be separated by standard technique known in the art.Due to the product at room temperature normally solid of formula 1, they are generally separated by filtration method, optionally can then use one or more organic solvents, such as, hexane, methyl alcohol, ethanol etc., cleaning is to remove unreacted glycol, and then under normal or reduced pressure, the baking oven that is placed in 30-100 ° of C is dry.The method of scheme 1 is set forth by following embodiment 1-12.
Embodiment
Abbreviation " E " representative " embodiment ", " CE " representative " comparative example ", its numeral below wherein prepares the numbering of the embodiment of polyester.Embodiment is prepared all in a similar manner and is tested.
material
All glycol and solvent all purchased from CTI, SigmaAldrich, AlfaAesar or SCRC, and directly use, without the need to being further purified.The dimethylbenzene adopted is the m-xylene of 60%, the p-Xylol of 14%, 9% of o-Xylol and the mixture of the ethylbenzene of 17%.Ruthenium catalyst, herein also referred to as " Ru catalyzer ", " Milstein catalyzer ", (carbonyl hydrogen [6-(two-tert-butyl phosphine-methylene radical)-2-(N, N-diethylamino methyl)-1,6-dihydropyridine] ruthenium (II), 98%, CASNo.863971-63-5) be purchased from StremChemicalInc..
testing method
1the collection of HNMR frequency spectrum uses Bruker400MHzAdvanceII spectrometer.The deuterated solvent used is DMSO-d 6.The report of chemical shift is the ppm that benchmark moves down (downfiled) with tetramethylsilane (TMS) displacement, and the report of coupling constant is in units of Hz; " s " means unimodal, and " d " means bimodal, and " t " means three peaks, and " q " is four peaks, and " m " means multimodal.
FTIR spectrum uses NicoletNEXUS5700 & ContinuumMicroscope spectrometer to obtain; Use rhombus ATR pattern; Detector: DTGS; Spectral range 4000 ~ 400cm -1.
Gpc measurement adopts gel permeation chromatography (GPC) instrument, uses eAlliance2695/2414RI detector to carry out under 35 ° of C.THF is elutriant, and injection flow speed is 1mL/min.Embodiment of the present invention limit further in the examples below.Before every measurement, GPC instrument standard polystyrene sample is calibrated.Be dissolved in testing sample in THF with the concentration of ~ 3mg/mL.
Differential scanning calorimetric (DSC) is carried out in the nitrogen atmosphere of drying with TAQ100 differential scanning calorimeter.First with the heating rate of 10 ° of C/min, sample is heated to 200 ° of C, keep at such a temperature 5 minutes to eliminate thermal history, next by its quenching to 0 ° C.Second-heating adopts the heating rate of 10 ° of C/min, operates obtain T to all test samples with this m(fusing point).T ctc, its can by cooling with the rate of cooling of 10 ° of C/min from melt temperature 200 ° of C time, observe occur exothermic maximum time temperature (Thermal release during crystallization) assess.
prepare the general step of polyester
Weigh glycol and ruthenium catalyst and be placed in round-bottomed flask.Introduce nitrogen gas stream slowly and provide nitrogen protection by connecting nitrogen balloon or Inlet gas connector on flask to reaction.
The mixture of glycol and catalyzer is heated to the temperature between 100 DEG C to 300 DEG C.The carrying out of reaction observes by disengaging of bubble along with hydrogen produces.Reaction mixture at least will heat 1 hour, is generally 8 hours or more of a specified duration.After the reaction times of specifying, this mixture is cooled to room temperature, no matter why, this reaction mixture generally all can solidify the degree of its dehydrogenation polymerization.
By the washing with alcohol 1 time of produced reaction mixture with about 50mL, then by the washing with alcohol 2 times of 50mL to remove unreacted glycol and/or oligopolymer.By remaining solids by filtering separation, and in vacuum drying oven at 50 DEG C dried overnight, weigh the product yield calculated.Polyester product passes through 1it is qualitative that HNMR, FTIR, GPC and DSC carry out analysis.The polyester of obtained formula 1 is by comprising 1the multiple characterizing method such as HNMR, FTIR, GPC and DSC confirms.
Embodiments of the present invention define in the following example further.
embodiment 1: prepare polyester by 1,5-PD
1,5-PD (2.982g, 30mmol) and Ru catalyzer (47.4mg, 0.1mmol) are weighed and is added into and be equipped with in 2 mouthfuls of reaction flasks (50mL) of condenser.Under magnetic stirring in 230 ° of C reacting by heating mixtures 8 hours.The crude mixture ethanol rinse of gained.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 1.791g polyester of the present invention (yield of 60%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.42-1.90(m,4H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ4.10(t,2H,-COO-CH 2-).
FTIR:3443.9,2956.4,2873.7,1732.6,1457.7,1419.7,1388.9,1384.9,1326.2,1280.4,1254.3,1182.1,1069.2,1046.3,977.4,750.8cm -1.
GPC:M n=6800g/mol,PDI=1.7.
DSC:T m=24.9°C,T c=-0.5°C.
embodiment 2: prepare polyester by decamethylene-glycol
Decamethylene-glycol (1.760g, 10mmol) and Ru catalyzer (22.6mg, 0.05mmol) are weighed and is added into single port reaction flask (50mL).Then reaction flask is used turned welt rubber stopper seal, and make it be connected with nitrogen balloon.Reacting by heating mixture 9.5 hours under 180 ° of C.Gained crude mixture ethanol rinse.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 1.34g polyester of the present invention (yield of 76%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.25-1.42(m,10H,-CH 2-),δ1.5-1.7(m,4H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ4.07(t,2H,-COO-CH 2-).
FTIR:3447.0,2923.9,2852.4,1733.7,1472.3,1415.6,1397.6,1376.1,1354.5,1294.3,1244.8,1215.1,1174.6,1118.5,1078.3,1048.5,1008.6,957.6,920.8,821.6,747.2,722.7,581.7cm -1.
GPC:M n=8000g/mol,PDI=1.6
DSC:T m=68.7°C,T c=57.8°C.
embodiment 3: prepare polyester by decamethylene-glycol
Decamethylene-glycol (1.760g, 10mmol) and Ru catalyzer (22.6mg, 0.05mmol) are weighed and is added into single port reaction flask (50mL).Then reaction flask is used turned welt rubber stopper seal, and make it be connected with nitrogen balloon.Reacting by heating mixture 24 hours under 180 ° of C.Gained crude mixture ethanol rinse.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 1.24g polyester of the present invention (yield of 70%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.25-1.42(m,10H,-CH 2-),δ1.5-1.7(m,4H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ4.07(t,2H,-COO-CH 2-).
FTIR:3447.7,2924.2,2852.7,1733.6,1472.4,1415.7,1397.9,1376.1,1354.9,1294.6,1244.9,1215.5,1175.1,1118.2,1078.5,1048.7,1008.9,958.0,921.0,821.6,747.3,722.8,582.2cm -1.
GPC:M n=7000g/mol,PDI=1.7
DSC:T m=68.1°C,T c=57.4°C.
embodiment 4: prepare polyester by decamethylene-glycol
Decamethylene-glycol (1.760g, 10mmol) and Ru catalyzer (22.6mg, 0.05mmol) are weighed and is added into single port reaction flask (50mL).Then reaction flask is used turned welt rubber stopper seal, and make it be connected with nitrogen balloon.Reacting by heating mixture 9 hours under 230-240 ° of C.Gained crude mixture ethanol rinse.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 1.05g polyester of the present invention (yield of 59%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.25-1.42(m,10H,-CH 2-),δ1.5-1.7(m,4H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ4.07(t,2H,-COO-CH 2-).
FTIR:3447.9,2923.1,2852.3,1733.6,1472.2,1415.6,1398.0,1376.1,1354.7,1294.3,1244.8,1215.2,1175.1,1118.3,1078.3,1048.6,1008.8,958.0,821.6,747.2,722.6,581.8cm -1.
GPC:M n=5250g/mol,PDI=1.4.
DSC:T m=66.5°C,T c=56.2°C.
embodiment 5: prepare polyester by decamethylene-glycol
Decamethylene-glycol (1.917g, 11mmol) and Ru catalyzer (10mg, 0.022mmol) are weighed and is added into single port reaction flask (50mL).Then reaction flask is used turned welt rubber stopper seal, and make it be connected with nitrogen balloon.Reacting by heating mixture 9 hours under 180 ° of C.Gained crude mixture ethanol rinse.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 1.048g polyester of the present invention (yield of 55%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.25-1.42(m,10H,-CH 2-),δ1.5-1.7(m,4H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ4.07(t,2H,-COO-CH 2-).
FTIR:3446.2,2922.5,2852.2,1733.7,1472.4,1415.5,1398.6,1376.1,1354.5,1294.5,1244.8,1215.2,1175.3,1118.4,1077.8,1048.4,1009.5,957.5,821.4,747.0,722.4,582.1cm -1.
GPC:M n=2800g/mol,PDI=1.3.
DSC:T m=62.4°C,T c=52.4°C.
embodiment 6: prepare polyester by decamethylene-glycol
Decamethylene-glycol (3.86g, 22mmol) and Ru catalyzer (10mg, 0.022mmol) are weighed and is added into single port reaction flask (50mL).Then reaction flask is used turned welt rubber stopper seal, and make it be connected with nitrogen balloon.Reacting by heating mixture 12.5 hours under 180 ° of C.Gained crude mixture ethanol rinse.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 2.09g polyester of the present invention (yield of 54%) under 50 ° of C.
1HNMR(CDCl3,400MHz):δ1.25-1.42(m,16H,-CH2-),δ1.5-1.7(m,8H,-CH2-),δ2.32(t,2H,-CH2-COO-),δ3.65(t,2H,-CH2-OH),δ4.07(t,2H,-COO-CH2-).
FTIR:3325.8,2921.4,2851.9,1733.6,1472.1,1415.3,1399.5,1376.1,1354.8,1294.3,1244.8,1215.3,1175.8,1118.2,1077.1,1048.4,1010.8,957.7,921.1,821.5,746.8,722.2,582.4cm -1.
GPC:M n=2300g/mol,PDI=1.3.
DSC:T m=63.4°C,T c=49.0°C.
embodiment 7: prepare polyester by decamethylene-glycol
Decamethylene-glycol (7.72g, 44mmol) and Ru catalyzer (10mg, 0.022mmol) are weighed and is added into single port reaction flask (50mL).Then reaction flask is used turned welt rubber stopper seal, and make it be connected with nitrogen balloon.Reacting by heating mixture 12.5 hours under 180 ° of C.Gained crude mixture ethanol rinse.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 4.69g polyester of the present invention (yield of 64%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.25-1.42(m,16H,-CH 2-),δ1.5-1.7(m,8H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ3.65(t,2H,-CH 2-OH),δ4.07(t,2H,-COO-CH 2-).
FTIR:3325.8,2921.4,2851.9,1733.6,1472.1,1415.3,1399.5,1376.1,1354.8,1294.3,1244.8,1215.3,1175.8,1118.2,1077.1,1048.4,1010.8,957.7,921.1,821.5,746.8,722.2,582.4cm -1.
GPC:M n=1960g/mol,PDI=1.5.
DSC:T m=60.8°C,T c=48.1°C.
comparative example 1: prepare polyester by decamethylene-glycol
Decamethylene-glycol (19.3g, 110mmol) and Ru catalyzer (5mg, 0.011mmol) are weighed and is added into single port reaction flask (50mL).Then reaction flask is used turned welt rubber stopper seal, and make it be connected with nitrogen balloon.Reacting by heating mixture 11.5 hours under 180 ° of C.Gained crude mixture ethanol rinse.After with ethanol rinse, do not have solid to be separated.
embodiment 8: prepare polyester by 1,12-dodecanediol
1,12-dodecanediol (1.78g, 8.8mmol) and Ru catalyzer (20mg, 0.022mmol) are weighed and is added into single port reaction flask (50mL).Then reaction flask is used turned welt rubber stopper seal, and make it be connected with nitrogen balloon.Reacting by heating mixture 48 hours under 150 ° of C.Gained crude mixture ethanol rinse.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 1.33g polyester of the present invention (yield of 75%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.29(m,14H,-CH 2-),δ1.62-1.64(m,4H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ4.07(t,2H,-COO-CH 2-).
FTIR:3448.7,2919.4,2850.9,1733.3,1471.8,1415.4,1397.6,1367.0,1329.8,1287.0,1271.4,1232.2,1206.1,1174.8,1118.4,1086.2,1061.9,1033.0,997.1,958.2,921.2,794.8,732.6,582.5cm -1.
GPC:M n=3740g/mol,PDI=2.4.
DSC:T m=76.4°C,T c=62.6°C.
embodiment 9: prepare polyester by decamethylene-glycol
By 1,10-decanediol (1.76g, 10mmol) weigh with Ru catalyzer (22.6mg, 0.05mmol) and be added into 2 mouthfuls of reaction flasks (50mL), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.After adding 3mL toluene (degassed before use), under magnetic stirring in 135 ° of C reacting by heating mixtures 24 hours.Gained crude mixture ethanol rinse.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 1.53g polyester of the present invention (yield of 87%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.31(m,10H,-CH 2-),δ1.6-1.7(m,4H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ4.07(t,2H,-COO-CH 2-).
FTIR:3447.8,2924.7,2852.7,1733.7,1472.4,1415.6,1397.6,1376.1,1354.4,1294.3,1244.8,1215.1,1174.8,1118.5,1078.4,1048.5,1008.5,957.5,921.1,857.3,747.3,722.6,582.4cm -1.
GPC:M n=7000g/mol,PDI=1.7.
DSC:T m=72.3°C,T c=57.9°C.
comparative example 2: prepare polyester by decamethylene-glycol
By 1,10-decanediol (1.76g, 10mmol) weigh with Ru catalyzer (22.6mg, 0.05mmol) and be added into 2 mouthfuls of reaction flasks (50mL), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.After adding 5mL toluene (degassed before use), under magnetic stirring in 135 ° of C reacting by heating mixtures 24 hours.Gained crude mixture ethanol rinse.Solid is not obtained with after ethanol rinse.
embodiment 10: prepare polyester by decamethylene-glycol
By 1,10-decanediol (1.76g, 10mmol) weigh with Ru catalyzer (22.6mg, 0.05mmol) and be added into 2 mouthfuls of reaction flasks (50mL), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.After adding the DMF (degassed before use) of 1mL, under magnetic stirring in 150 ° of C reacting by heating mixtures 24 hours.By gained crude mixture alcohol settling and rinsing.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 0.445g polyester of the present invention (yield of 25%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.31(m,10H,-CH 2-),δ1.61-1.65(m,4H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ4.07(t,2H,-COO-CH 2-).
FTIR:3447.8,2924.7,2852.7,1733.7,1472.4,1415.6,1397.6,1376.1,1354.4,1294.3,1244.8,1215.1,1174.8,1118.5,1078.4,1048.5,1008.5,957.5,921.1,857.3,747.3,722.6,582.4cm -1.
GPC:M n=2500g/mol,PDI=1.1.
DSC:T m=64.0°C,T c=52.0°C.
comparative example 3: prepare polyester by decamethylene-glycol
By 1,10-decanediol (1.76g, 10mmol) weigh with Ru catalyzer (22.6mg, 0.05mmol) and be added into 2 mouthfuls of reaction flasks (50mL), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.After adding 5mLDMF (degassed before use), under magnetic stirring in 150 ° of C reacting by heating mixtures 24 hours.Gained crude mixture ethanol rinse.Solid is not obtained with after ethanol rinse.
embodiment 11: prepare polyester by 1,12-dodecanediol
By 1,12-dodecanediol (1.78g, 8.8mmol) weigh with Ru catalyzer (20mg, 0.044mmol) and be added into 2 mouthfuls of reaction flasks (50mL), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.After adding 2mL dimethylbenzene (degassed before use), under magnetic stirring in 150 ° of C reacting by heating mixtures 48 hours.Gained crude mixture ethanol rinse.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 1.602g polyester of the present invention (yield of 90%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.29(m,14H,-CH 2-),δ1.62-1.64(m,4H,-CH 2-),δ2.32(t,2H,-CH 2-COO-),δ4.07(t,2H,-COO-CH 2-).
FTIR:3448.2,2919.0,2850.7,1732.9,1468.8,1415.5,1397.1,1366.8,1329.7,1271.2,1232.2,1205.9,1173.9,1117.4,1086.0,1062.0,1033.1,997.2,958.2,921.0,794.7,721.9,582.7cm -1.
GPC:M n=22000g/mol,PDI=1.9.
DSC:T m=80.7°C,T c=64.4°C
embodiment 12: prepare polyester by 1,4 cyclohexane dimethanol
By 1,4-cyclohexanedimethanol (1.3g, 8.8mmol) weigh with Ru catalyzer (20mg, 0.044mmol) and be added into 2 mouthfuls of reaction flasks (50mL), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.After adding 2mL dimethylbenzene (degassed before use), under magnetic stirring in 150 ° of C reacting by heating mixtures 48 hours.By gained crude mixture alcohol settling and rinsing.Rinsed solid is via filtering separation, and drying under reduced pressure whole night, obtains 1.17g polyester of the present invention (yield of 90%) under 50 ° of C.
1HNMR(CDCl 3,400MHz):δ1.21-1.92(m,8H);δ2.03-2.59(m,2H),δ3.90-4.02(m,2H,-COO-CH 2-)
FTIR:3438.6,2936.5,2857.6,1727.9,1450.8,1391.6,1321.0,1249.8,1230.2,1175.8,1138.2,1037.0,933.2,899.5,770.0,673.9,597.7cm -1.
GPC:M n=3280g/mol,PDI=2.0.
DSC:T g=30.8°C,T m=150.7°C.
Table 1 summarizes the reaction details of the embodiment 1-12 according to the inventive method.Also list in wherein for the ease of comparison comparative example 1-3.
Table 1
Embodiment 1-12 demonstrates method of the present invention and is suitable for the dehydrogenation polyesterification of the glycol of various formula 2 to prepare various aliphatic polyester.In addition, method of the present invention has no particular limits temperature of reaction, and it spans a wide region (namely from 135 DEG C of embodiment 9 to 240 DEG C of embodiment 4).Similar conclusion also can obtain from its reaction times, and its scope is little of 48 hours from 8.
In a word, method of the present invention is prepared under low effective catalyst load for various aliphatic polyester has very large business potential, and provides the processing procedure more clean relative to conventional polyester method and have the method for atom economy.
Although the present invention is illustrated with typical embodiment and describes, and do not mean that it is limited in shown details, because multiple amendment may be there is under spirit of the present invention and substitutes not deviating from.Thus, when those skilled in the art only use normal experiment just can obtain with the improvement of invention disclosed herein and be equal to, and believe that these improve and are equal in the spirit and scope of the present invention defined all in the claims.

Claims (10)

1. the preparation method of the polyester of formula 1,
Described method comprises:
The glycol of (a) hybrid 2, the ruthenium catalyst of formula 3
With solvent or the solvent systems of optional existence, with forming reactions mixture; And
B described reaction mixture, under temperature is the scope of 100-300 DEG C, is heated 1-60 hour to form the polyester of formula 1 by ();
Wherein:
A is-(CH 2) p-W q-(CH 2) r-, wherein W is selected from C 3-C 10cycloalkyl, p is the integer of 1 to 8, q be 0 or 1, r be 1 to 8 integer, and when q is 0, the summation of p and r is the integer of 3 to 14;
The summation of k and n is the integer of 10 to 150,
L 1and L 2be selected from P (R independently of one another 1) 2, P (OR 2) 2with N (R 3) 2group;
L 3be selected from CO, P (R 1) 3, P (OR 2) 3, NO +, nitrile (R 4and isonitrile ((R CN) 5nC) bielectron list coordinating donor; And
R 1, R 2, R 3, R 4and R 5it is the group being selected from alkyl, cycloalkyl, aryl, alkylaryl, heterocyclic radical and heteroaryl independently of one another.
2. method according to claim 1, wherein L 1p (R 1) 2, L 2n (R 3) 2, and L 3cO.
3. method according to claim 2, wherein R 1the tertiary butyl, and R 3it is ethyl.
4. method according to claim 1, the glycol of the formula 2 of amount relative to every mole of the ruthenium catalyst of wherein said formula 3 is 0.05 % by mole to 5 % by mole.
5. method according to claim 1, the glycol of wherein said formula 2 is C 5-C 16alkyl diol, C 5-C 16cycloalkylalkyl glycol or its mixture.
6. method according to claim 5, the glycol of wherein said formula 2 is selected from 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, decamethylene-glycol, 1,12-dodecanediol, 1,14-tetradecane diols, 1,16-hexadecane diol, 1,3-CHDM, 1,4 cyclohexane dimethanol, 1,4-hexanaphthene di-alcohol, Isosorbide-5-Nitrae-hexanaphthene two propyl alcohol and its mixture.
7. method according to claim 1, wherein said solvent or solvent system are selected from hexanaphthene, benzene, toluene, p-Xylol, m-xylene, o-Xylol, phenylmethylether, sym-trimethylbenzene, tetrahydrofuran (THF), 1,2-glycol dimethyl ether, Isosorbide-5-Nitrae-diox, diglyme, dimethyl formamide, methyl-sulphoxide and its mixture.
8. method according to claim 1, the glycol of the formula 2 of scope relative to every mole of the amount of wherein said solvent or solvent system is 0.01L to 0.45L.
9. method according to claim 1, the polyester of wherein said formula 1 is formed under inert gas atmosphere, and the pressure of described rare gas element is 1bar to 10bar.
10. the polyester of formula 1, the polyester of described formula 1 is obtained by the method according to any one of claim 1-9,
Wherein:
A is-(CH 2) p-W q-(CH 2) r-, wherein W is selected from C 3-C 10cycloalkyl, p is the integer of 1 to 8, q be 0 or 1, r be 1 to 8 integer, and when q is 0, the summation of p and r is the integer of 3 to 14; And
The summation of k and n is the integer of 10 to 150.
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