CN103897157A - A method of preparing aliphatic polyester from diol - Google Patents

A method of preparing aliphatic polyester from diol Download PDF

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Publication number
CN103897157A
CN103897157A CN201210572950.2A CN201210572950A CN103897157A CN 103897157 A CN103897157 A CN 103897157A CN 201210572950 A CN201210572950 A CN 201210572950A CN 103897157 A CN103897157 A CN 103897157A
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glycol
formula
polyester
integer
solvent
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CN103897157B (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

Abstract

The invention discloses a method of preparing aliphatic polyester from diol. The method includes heating a mixture comprising the diol, a ruthenium catalyst and an optional solvent or an optional solvent system. According to the method, the aliphatic polyester can be prepared with high yield by heating the mixture at 100-300 DEG C for 1-60 h.

Description

Prepared the method for aliphatic polyester by glycol
Technical field
The present invention relates to directly be prepared by glycol the method for aliphatic polyester under the existence of ruthenium catalyst.
Background technology
Polyester is formed by diacid and glycol polycondensation conventionally.Commercialization polyester synthetic is usually directed to two steps: (1) condensation/transesterify: diacid or its ester and excessive glycol are reacted to form oligopolymer at relatively low temperature, remove continuously volatile small molecules simultaneously, for example, water, ethanol or methyl alcohol; (2) polymerization: oligopolymer is heated under certain high temperature to (for example polymerization of phthalic acid glycol ester is to carry out) and remove more volatile excess monomer under 250 ° of C under negative pressure, be often glycol, thereby obtain the polyester of high molecular.The main drawback of condensation polymerization method is under high vacuum He under high temperature, to remove unnecessary monomer, and this can increase cost of energy and cause the possible degraded of polyester product.
In addition, polyester also can be prepared by the ring-opening polymerization of cyclic lactone.For example, polycaprolactone is by ring-opening polymerization caprolactone, and it is a kind of cyclic ester monomer, commercially produces.The multipolymer of ester also can be prepared by the mixing of cyclic lactone monomer is carried out to ring-opening polymerization, sees that N.Nomura et al is at JACS2010, and 132,1750-1751 is disclosed.
Recently, the people such as Milstein are at Science2007, disclose by using Ru(ruthenium in 317,790) catalyzer can be its unique by product from the synthetic various esters of various alcohol release hydrogen.This catalytic dehydrogenation esterification process provides a lot of advantages, 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.In the time describing polyester, described polyester is normally described based on monomer used.For example, PGA or polyglycolic acid (PGA) are aliphatic polyesters, and it is the condensation preparation by oxyacetic acid; And polyethylene terephthalate (PET) is semi-aromatic polyester, it is the polycondensation preparation by terephthalic acid and ethylene glycol.
Consider that aliphatic polyester is as the biodegradable characteristic of PGA, this kind polyester is just receiving more concern recently.Therefore any improvement, obtaining in its production technique is all welcome.Applicant's discovery of the present invention, aliphatic polyester can be from various glycol by similar dehydrogenation polymerization method preparation.Described polymerization can be carried out under the existence of solvent, or can under condition of no solvent, carry out.
Summary of the invention
The invention provides a kind of method of the polyester for the preparation of formula 1,
Figure BDA00002650803800021
Described method comprises:
(a) ruthenium catalyst of hybrid 2 glycol, formula 3
Figure BDA00002650803800022
With solvent or the solvent systems of optional existence, to form reaction mixture; And
(b) under temperature is the scope of 100-300 DEG C, by described reaction mixture heating 1-60 hour to form the polyester of formula 1;
Wherein:
A is-(CH 2) p-W q-(CH 2) r-, wherein W is selected from C 3-C 10cycloalkyl, p is 1 to 8 integer, q be 0 or 1, r be 1 to 8 integer, and in the time that q is 0, the summation of p and r is 3 to 14 integer;
The summation of k and n is 10 to 150 integer;
L 1and L 2to be selected from independently of one another P (R 1) 2, P (OR 2) 2and N (R 3) 2group;
L 3to be selected from CO, P (R 1) 3, P (OR 2) 3, NO +, nitrile (R 4and isonitrile ((R CN) 5nC) bielectron list coordination is to body; And
R 1, R 2, R 3, R 4and R 5it is the group that is selected from independently of one another alkyl, cycloalkyl, aryl, alkylaryl, heterocyclic radical and heteroaryl.
Method of the present invention will be described in further detail hereinafter.In following scheme, except as otherwise noted, each definition as above limits.
Embodiment
All publications mentioned in this article, patent application, patent and other reference, if not contrary explanation all its full content is quoted clearly and is added herein, as them in this article by full disclosure.
Unless otherwise defined, all technology used herein and scientific terminology have the identical implication of conventionally understanding with one skilled in the art of the present invention.In the time 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 any other distortion, is intended to cover comprising of non-exclusionism.For example, the composition, step, method, goods or the device that comprise listed key element needn't only limit to those key elements, but can comprise other key element or this kind of key element that composition, step, method, goods or device are intrinsic clearly do not listed.
Conjunction " by ... composition " get rid of any key element of not pointing out, step or component.If for claim, it is closed that this phrase will make claim, makes it not comprise the material except the material of those descriptions, but except relative conventional impurity.In the time that phrase " by ... composition " appears in the clause of claim main body instead of immediately after theme, it is only limited to the key element of describing 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 comprise except those words discuss material, step, feature, component or key element, prerequisite is the basic and novel characteristic of can the materially affect not claimed invention of these additional materials, step, feature, component or key element.Term " substantially by ... composition " position rank 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 by the embodiment that comprises of 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 are 1 to 16 numerical value.
In one embodiment, term " alkyl " is using separately or during as another group a part of, refer to " C 1to C 16alkyl ", and refer to linear and cladodification, saturated or unsaturated (for example thiazolinyl, alkynyl) group, unsaturated group is situation about being only applicable in the time that 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 groups, described substituting group is to be 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 further replaced by above-mentioned arbitrary substituting group.As an example, " alkoxyalkyl " is the alkyl that alkoxy replaces.
Herein term " cycloalkyl " uses separately or during as another group a part of, refers to " C 3to C 10cycloalkyl " and refer to saturated or undersaturated (for example cycloalkenyl group, cycloalkynyl radical) monocycle or many cyclic groups.The limiting examples of cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, two ring [2.2.1] heptyl, two ring [2.2.2] octyl group or adamantyls.The example of cycloalkenyl group comprises cyclopentenyl, cyclohexenyl etc.Cycloalkyl can be unsubstituted, or is replaced by one or more substituting groups, and described substituting group is as defined in the above-mentioned substituting group to alkyl.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 " uses separately or during as another group a part of, refers to the aromatic ring system that contains 6-14 one-tenth ring carbon atom.Aryl rings can be monocycle, dicyclo, three rings etc.The limiting examples of aryl is that phenyl, naphthyl comprise 1-naphthyl and 2-naphthyl etc.Aryl can be unsubstituted or by can substituted carbon atom by one or more as above-mentioned the group that alkyl limited is replaced.Aralkyl represents to be bonded to the aryl (for example benzyl) of alkyl.
Herein term " heteroaryl " uses separately or during as another group a part of, it is heteroatomic heteroaromatic system that expression comprises at least one annular atoms, and described heteroatoms is to be selected from nitrogen, sulphur and oxygen.Heteroaryl comprises 5 or more one-tenth annular atoms.Heteroaryl can be monocycle, dicyclo, three rings etc.Heteroaryl also comprises benzheterocycle.If nitrogen is into annular 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 can substituted atom by one or more as above-mentioned the group that alkyl limited is replaced.
When term " heterocycle " or " heterocyclic radical " uses separately or uses as a part for another group, represent to have 1 to 4 heteroatomic ternary to octatomic ring herein, 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, sulfo-pyranyl, piperazinyl, indyl, dihydrofuran base, tetrahydrofuran base, dihydro-thiophene base, tetrahydro-thienyl, dihydro pyranyl, THP trtrahydropyranyl etc.Heterocyclic radical can be unsubstituted, or as above-mentioned, the group that alkyl limited is replaced by one or more by available atom.
All be applicable to have described in this specification sheets and claim the corresponding various groups in the compound of formula 1, formula 2, formula 3 and formula 4 for the restriction of various groups and preferable range above.
When 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 limit preferred value, this is appreciated that and specifically discloses all scopes that formed by arbitrary pairing of any range limit or preferred value and any scope lower limit or preferred value, no matter and whether this scope discloses separately.For example, in the time 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.In the time that numerical range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers and mark within the scope of this.
In the time that term " about " is used to describe the end value of numerical value or scope, describedly openly should be understood to include concrete numerical value or the end value that it relates to.
In addition, unless there is clear and definite contrary instruction, "or" refers to the "or" of comprising property instead of the "or" of exclusiveness.For example, any form A "or" B:A that all satisfies condition is that true (or existence) and B are pseudo-(or not existing) below, A for pseudo-(or not existing) and B be true (or existence), and A and B are very (or existence).
In addition the indefinite article " one " before key element of the present invention or component and " one " quantitative requirement (the being occurrence number) unrestriction to 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 being obtained by a kind of polymerization of repeating unit.Term " multipolymer " refers to the polymkeric substance that comprises the copolymerization units being obtained by two or more comonomer copolymerization." copolymer " refer to substantially by the polymkeric substance of cell formation that is derived from two kinds of comonomers, and " terpolymer " refers to substantially by the multipolymer of cell formation that is derived from three kinds of comonomers.For example, 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: describe the method for 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: describe the method for 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: describe the method for the polyester of preparation formula 1 in summary of the invention, wherein L 3cO.
Embodiment 6: describe the method for the polyester of preparation formula 1 in summary of the invention, the glycol of the described formula 2 of the scope of the amount of the ruthenium catalyst of wherein said formula 3 with respect to every mole is approximately 0.05 % by mole to approximately 5 % by mole.
Embodiment 7: the method for embodiment 6, the glycol of the described formula 2 of the scope of the amount of the ruthenium catalyst of wherein said formula 3 with respect to every mole is approximately 0.1 % by mole to approximately 1 % by mole.
Embodiment 8: the method for embodiment 7, the glycol of the described formula 2 of the scope of the amount of the ruthenium catalyst of wherein said formula 3 with respect to every mole is approximately 0.2 % by mole to approximately 0.8 % by mole.
Embodiment 9: the method for 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-dioxs, diglyme, dimethyl formamide, methyl-sulphoxide and its mixture.
Embodiment 10: describe the method for the polyester of preparation formula 1 in summary of the invention, the glycol of the described formula 2 of the scope of the amount of wherein said solvent or solvent system with respect to every mole is that about 0.01L is to about 0.45L.
Embodiment 11: the method for embodiment 10, the glycol of the described formula 2 of the scope of the amount of wherein said solvent or solvent system with respect to every mole is that about 0.1L is to about 0.4L.
Embodiment 12: describe the method for the polyester of preparation formula 1 in summary of the invention, wherein the polyester of wherein said formula 1 forms under inert gas atmosphere.
Embodiment 13: the method for embodiment 12, the polyester of wherein said formula 1 is to form to the pressure of about 10bar at about 1bar.
Embodiment 14: the method for embodiment 13, the polyester of wherein said formula 1 is to form to the pressure of about 5bar at about 1bar.
Embodiment 15: the method for embodiment 14, the polyester of wherein said formula 1 is to form under the pressure that approaches normal atmosphere (An).
Embodiment 16: describe the method for the polyester of preparation formula 1 in summary of the invention, wherein said heating is to carry out to the temperature range of approximately 260 ° of C at approximately 120 ° of C.
Embodiment 17: describe the method for 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 to be selected from 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, decamethylene-glycol, 1,12-dodecanediol, 1,14-tetradecane glycol, 1,16-n-Hexadecane glycol, 1,3-CHDM, 1,4 cyclohexane dimethanol, 1,4-hexanaphthene di-alcohol, Isosorbide-5-Nitrae-hexanaphthene two propyl alcohol and its mixture.
As described in summary of the invention part, embodiments of the present invention comprise any other embodiment 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 or the solvent systems that the glycol of formula 2 are contacted and optionally exist with the ruthenium catalyst of formula 3.
scheme 1
Figure BDA00002650803800071
glycol
The glycol of multiple formula 2 can be used for, in method of the present invention, comprising C 5-C 16alkyl diol is (when A is-(CH 2) p-W q-(CH 2) r-, q is 0, and p and r's and while being 3 to 14 integer); C 5-C 16cycloalkylalkyl glycol (in the time that q is 1).
Figure BDA00002650803800081
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 glycol, 1,12-dodecanediol, 1,13-tridecane glycol, 1,14-tetradecane glycol, 1,15-pentadecane glycol or 1,16-n-Hexadecane glycol.
C 5-C 16the example of cycloalkylalkyl glycol is 1, 2-cyclopropane dimethanol, 1, 2-tetramethylene dimethanol, 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 ring [2.2.1] heptane-2, 3-dimethanol, two ring [2.2.2] octane-1, 4-dimethanol, two ring [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 can be 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 glycol, 1,16-n-Hexadecane glycol, 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 glycol, 1,16-n-Hexadecane glycol, 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 is by the ruthenium of formula 3 (Ru) complex catalysis, without alkali or acid cocatalyst.
Figure BDA00002650803800091
In a preferred embodiment, Ru catalyzer is by the compounds represented of formula 3a:
Figure BDA00002650803800092
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 1the tertiary butyl and R 3be ethyl by formula 3b compounds represented, its commercially available Strem Chemical Inc. that derives from.
What can understand is in the time that catalyzer comprises one or more chiral centre, and all steric isomers are also included within scope of the present invention.
Method of the present invention is carried out conventionally under the existence of ruthenium catalyst, and the amount of ruthenium catalyst is approximately 0.05 % by mole-Yue 5 % by mole with respect to the glycol of every mole of formula 2, or approximately 0.1 % by mole-Yue 1 % by mole or approximately 0.2 % by mole-Yue 0.8 % by mole.
the solvent of reaction
Method of the present invention can be carried out under the condition of solvent or solvent systems existence.Described " solvent systems " is to 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-dioxs, diglyme, dimethyl formamide (DMF), methyl-sulphoxide (DMSO) or its mixture.
Method of the present invention also can be carried out under solvent-free condition.Term " solvent-free " or " not containing solvent " are used interchangeably in this article; It means in the methods of the invention, described reaction mixture, and the gross weight meter based on reaction mixture, contains the solvent that is 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 in solvent or the dispensable situation of solvent systems.
For processing ease, first the glycol of formula 2 is joined in reaction vessel.Conventionally room temperature and rare gas element as nitrogen or argon gas atmosphere under, Ru catalyzer is joined in the reaction vessel of the glycol that contains formula 2.If use solvent or solvent system, it is finally just to add.
As shown in scheme 1, it is by product that described method can produce hydrogen.Because reaction is at high temperature carried out conventionally, the hydrogen that great majority generate can disengage from reaction mixture.Described reaction conventionally, under standard pressure (about 1bar), has under stable inert gas flow and carries out, and the hydrogen generating in reaction process can be blown away, to avoid accumulating the hydrogen of high density in reaction vessel.
Temperature of reaction has no particular limits, and condition is that it is at least than the low 10 ° of C of the boiling point of glycol, to avoid the loss of reactant.If have solvent or solvent system to exist, temperature of reaction can be up to the reflux temperature of this reaction mixture.Described temperature of reaction conventionally between approximately 100 ° of C between approximately 300 ° of C, be preferably between approximately 120 ° of C between approximately 260 ° of C.
Depend on batch scale and the temperature of reaction using, those skilled in the art can determine the time that reaction is carried out aptly.
The product of formula 1 can separate by standard technique known in the art.Due at room temperature solid normally of the product of formula 1, they generally can separate by filtration method, optionally can then use one or more organic solvents, for example, hexane, methyl alcohol, ethanol etc., clean to remove unreacted glycol, then under normal pressure or decompression, 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 is wherein prepared the numbering of the embodiment of polyester.Embodiment all prepares in a similar manner and tests.
material
All glycol and solvent be all purchased from CTI, Sigma Aldrich, and Alfa Aesar or SCRC, and directly use, without being further purified.The dimethylbenzene adopting is 60% m-xylene, 14% p-Xylol, the mixture of 9% and 17% ethylbenzene of o-Xylol.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%, CAS No.863971-63-5) be purchased from Strem Chemical Inc..
testing method
1the collection of H NMR frequency spectrum is used Bruker400MHz Advance II spectrometer.The deuterated solvent using is DMSO-d 6.The report of chemical shift moves down the ppm of (downfiled) taking tetramethylsilane (TMS) displacement as benchmark, the report of coupling constant is taking Hz as unit; " s " means unimodal, and " d " means bimodal, and " t " means three peaks, and " q " is four peaks, and " m " means multimodal.
FTIR spectrum uses Nicolet NEXUS5700 & Continuum Microscope 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 further limit in following examples.Before each measurement, GPC instrument is calibrated with polystyrene standard sample.Be dissolved in THF with the concentration of ~ 3mg/mL testing sample.
Poor formula scanning calorimetric (DSC) is carried out in dry nitrogen atmosphere with TA Q100 differential scanning calorimeter.First with the heating rate of 10 ° of C/min, sample is heated to 200 ° of C, remains on lower 5 minutes of this temperature to eliminate thermal history, next by its quenching to 0 ° C.Second-heating adopts the heating rate of 10 ° of C/min, operates all test samples are obtained to T with this m(fusing point).T cbe Tc, it can carry out when cooling with the rate of cooling of 10 ° of C/min by starting from 200 ° of C of melt temperature, and the temperature (heat during crystallization discharges) of observing while there is exothermic maximum is assessed.
prepare the general step of polyester
Weigh glycol and ruthenium catalyst and be placed in round-bottomed flask.Introduce slowly nitrogen gas stream and provide nitrogen protection to reaction by connect nitrogen balloon or Inlet gas connector on flask.
The mixture of glycol and catalyzer is heated to the temperature between 100 DEG C to 300 DEG C.What react is to be accompanied by hydrogen produce and can observe by disengaging of bubble.Reaction mixture at least will heat 1 hour, is generally 8 hours or more of a specified duration.Arrived after the reaction times of specifying, this mixture is cooled to room temperature, no matter the degree of its dehydrogenation polymerization why, and this reaction mixture generally all can solidify.
By the washing with alcohol of about 50mL 1 time for produced reaction mixture, then by the washing with alcohol of 50mL 2 times to remove unreacted glycol and/or oligopolymer.By remaining solids by filtering separation, and in vacuum drying oven at 50 DEG C dried overnight, the product yield of weighing to calculate.Polyester product is to pass through 1h NMR, FTIR, GPC and DSC analyze qualitative.The polyester of the formula 1 making is by comprising 1the multiple characterizing methods such as H NMR, FTIR, GPC and DSC are confirmed.
Embodiments of the present invention are further defined in following embodiment.
embodiment 1: prepare polyester by 1,5-PD
1,5-PD (2.982g, 30mmol) and Ru catalyzer (47.4mg, 0.1mmol) are weighed and be added in 2 mouthfuls of reaction flasks (50mL) that condenser is housed.Under magnetic agitation in 230 ° of C reacting by heating mixtures 8 hours.The ethanol rinsing of the crude mixture of gained.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 1.791g polyester of the present invention (60% yield) under 50 ° of C.
1H?NMR(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 be added into single port reaction flask (50mL).Then reaction flask is used to turned welt rubber stopper seal, and it is connected with nitrogen balloon.Reacting by heating mixture 9.5 hours under 180 ° of C.The ethanol rinsing of gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 1.34g polyester of the present invention (76% yield) under 50 ° of C.
1H?NMR(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 be added into single port reaction flask (50mL).Then reaction flask is used to turned welt rubber stopper seal, and it is connected with nitrogen balloon.Reacting by heating mixture 24 hours under 180 ° of C.The ethanol rinsing of gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 1.24g polyester of the present invention (70% yield) under 50 ° of C.
1H?NMR(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 be added into single port reaction flask (50mL).Then reaction flask is used to turned welt rubber stopper seal, and it is connected with nitrogen balloon.Reacting by heating mixture 9 hours under 230-240 ° of C.The ethanol rinsing of gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 1.05g polyester of the present invention (59% yield) under 50 ° of C.
1H?NMR(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 be added into single port reaction flask (50mL).Then reaction flask is used to turned welt rubber stopper seal, and it is connected with nitrogen balloon.Reacting by heating mixture 9 hours under 180 ° of C.The ethanol rinsing of gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 1.048g polyester of the present invention (55% yield) under 50 ° of C.
1H?NMR(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 be added into single port reaction flask (50mL).Then reaction flask is used to turned welt rubber stopper seal, and it is connected with nitrogen balloon.Reacting by heating mixture 12.5 hours under 180 ° of C.The ethanol rinsing of gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 2.09g polyester of the present invention (54% yield) under 50 ° of C.
1H?NMR(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 be added into single port reaction flask (50mL).Then reaction flask is used to turned welt rubber stopper seal, and it is connected with nitrogen balloon.Reacting by heating mixture 12.5 hours under 180 ° of C.The ethanol rinsing of gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 4.69g polyester of the present invention (64% yield) under 50 ° of C.
1H?NMR(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 be added into single port reaction flask (50mL).Then reaction flask is used to turned welt rubber stopper seal, and it is connected with nitrogen balloon.Reacting by heating mixture 11.5 hours under 180 ° of C.The ethanol rinsing of gained crude mixture.With not having solid to be separated after ethanol rinsing.
embodiment 8: prepare polyester by 1,12-dodecanediol
1,12-dodecanediol (1.78g, 8.8mmol) and Ru catalyzer (20mg, 0.022mmol) are weighed and be added into single port reaction flask (50mL).Then reaction flask is used to turned welt rubber stopper seal, and it is connected with nitrogen balloon.Reacting by heating mixture 48 hours under 150 ° of C.The ethanol rinsing of gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 1.33g polyester of the present invention (75% yield) under 50 ° of C.
1H?NMR(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 and be added into 2 mouthfuls of reaction flasks (50mL) with Ru catalyzer (22.6mg, 0.05mmol), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.Add after 3mL toluene (use before degassed), under magnetic agitation in 135 ° of C reacting by heating mixtures 24 hours.The ethanol rinsing of gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 1.53g polyester of the present invention (87% yield) under 50 ° of C.
1H?NMR(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 and be added into 2 mouthfuls of reaction flasks (50mL) with Ru catalyzer (22.6mg, 0.05mmol), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.Add after 5mL toluene (use before degassed), under magnetic agitation in 135 ° of C reacting by heating mixtures 24 hours.The ethanol rinsing of gained crude mixture.With not obtaining solid after ethanol rinsing.
embodiment 10: prepare polyester by decamethylene-glycol
By 1,10-decanediol (1.76g, 10mmol) weigh and be added into 2 mouthfuls of reaction flasks (50mL) with Ru catalyzer (22.6mg, 0.05mmol), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.Add after the DMF (use before degassed) of 1mL, under magnetic agitation in 150 ° of C reacting by heating mixtures 24 hours.By ethanol precipitation and rinsing for gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 0.445g polyester of the present invention (25% yield) under 50 ° of C.
1H?NMR(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 and be added into 2 mouthfuls of reaction flasks (50mL) with Ru catalyzer (22.6mg, 0.05mmol), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.Add after 5mL DMF (use before degassed), under magnetic agitation in 150 ° of C reacting by heating mixtures 24 hours.The ethanol rinsing of gained crude mixture.With not obtaining solid after ethanol rinsing.
embodiment 11: prepare polyester by 1,12-dodecanediol
By 1,12-dodecanediol (1.78g, 8.8mmol) weigh and be added into 2 mouthfuls of reaction flasks (50mL) with Ru catalyzer (20mg, 0.044mmol), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.Add after 2mL dimethylbenzene (use before degassed), under magnetic agitation in 150 ° of C reacting by heating mixtures 48 hours.The ethanol rinsing of gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 1.602g polyester of the present invention (90% yield) under 50 ° of C.
1H?NMR(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 and be added into 2 mouthfuls of reaction flasks (50mL) with Ru catalyzer (20mg, 0.044mmol), this flask is equipped with condenser and the junctor for stream of nitrogen gas entrance at top.Add after 2mL dimethylbenzene (use before degassed), under magnetic agitation in 150 ° of C reacting by heating mixtures 48 hours.By ethanol precipitation and rinsing for gained crude mixture.The solid of rinsing is via filtering separation, and drying under reduced pressure whole night, obtains 1.17g polyester of the present invention (90% yield) under 50 ° of C.
1H?NMR(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 has been summed up according to the reaction details of the embodiment 1-12 of the inventive method.For the ease of comparison comparative example, 1-3 also lists in wherein.
Table 1
Figure BDA00002650803800181
Embodiment 1-12 has proved that the dehydrogenation polyesterification of glycol that method of the present invention is suitable for various formulas 2 is to prepare various aliphatic polyesters.In addition, method of the present invention has no particular limits temperature of reaction, and it has crossed over a wide region (i.e. 240 DEG C from 135 DEG C of embodiment 9 to embodiment 4).Similarly conclusion also can obtain from its reaction times, and its scope was from 8 hours to 48 hours.
In a word, method of the present invention is prepared and has very large business potential under low effective catalyst load for various aliphatic polyesters, and the processing procedure more clean with respect to traditional polyesterification method is provided and has had the method for atom economy.
Although the present invention is illustrated and describes with typical embodiment, and do not mean that it is limited in shown details, because may have multiple amendment under spirit of the present invention and substitute not deviating from.Thus, just can obtain with the improvement of invention disclosed herein and be equal to when those skilled in the art only use normal experiment, and believe these improvement and be equal to all in the claims in defined the spirit and scope of the present invention.

Claims (10)

1. the preparation method of the polyester of formula 1,
Figure FDA00002650803700011
Described method comprises:
(a) ruthenium catalyst of hybrid 2 glycol, formula 3
Figure FDA00002650803700012
With solvent or the solvent systems of optional existence, to form reaction mixture; And
(b) under temperature is the scope of 100-300 DEG C, by described reaction mixture heating 1-60 hour to form the polyester of formula 1;
Wherein:
A is-(CH 2) p-W q-(CH 2) r-, wherein W is selected from C 3-C 10cycloalkyl, p is 1 to 8 integer, q be 0 or 1, r be 1 to 8 integer, and in the time that q is 0, the summation of p and r is 3 to 14 integer;
The summation of k and n is 10 to 150 integer,
L 1and L 2to be selected from independently of one another P (R 1) 2, P (OR 2) 2and N (R 3) 2group;
L 3to be selected from CO, P (R 1) 3, P (OR 2) 3, NO +, nitrile (R 4and isonitrile ((R CN) 5nC) bielectron list coordination is to body; And
R 1, R 2, R 3, R 4and R 5it is the group that is selected from independently of one another alkyl, cycloalkyl, aryl, alkylaryl, heterocyclic radical and heteroaryl.
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 the amount of the ruthenium catalyst of wherein said formula 3 with respect to every mole 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 to be selected from 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, decamethylene-glycol, 1,12-dodecanediol, 1,14-tetradecane glycol, 1,16-n-Hexadecane glycol, 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-dioxs, diglyme, dimethyl formamide, methyl-sulphoxide and its mixture.
8. method according to claim 1, the glycol of the formula 2 of the scope of the amount of wherein said solvent or solvent system with respect to every mole is 0.01L to 0.45L.
9. method according to claim 1, the polyester of wherein said formula 1 forms 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 makes by the method described in any one in claim 1-9,
Figure FDA00002650803700031
Wherein:
A is-(CH 2) p-W q-(CH 2) r-, wherein W is selected from C 3-C 10cycloalkyl, p is 1 to 8 integer, q be 0 or 1, r be 1 to 8 integer, and in the time that q is 0, the summation of p and r is 3 to 14 integer; And
The summation of k and n is 10 to 150 integer.
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