CN103626995A - Preparation method for polyamides from glycol and diamine - Google Patents
Preparation method for polyamides from glycol and diamine Download PDFInfo
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- CN103626995A CN103626995A CN201210299579.7A CN201210299579A CN103626995A CN 103626995 A CN103626995 A CN 103626995A CN 201210299579 A CN201210299579 A CN 201210299579A CN 103626995 A CN103626995 A CN 103626995A
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Abstract
The invention discloses a solvent-free preparation method for polyamides. According to the method, glycol reacts with diamine in the presence of a ruthenium catalyst with a concentration of 0.01 mol% to 5 mol%; the reaction is carried out at a temperature in a range of 130 DEG C to 300 DEG C, and a variety of aliphatic polyamides and non-aliphatic polyamides are obtained.
Description
Technical field
The present invention relates to by direct coupling glycol and diamines, prepare the no-solvent process of polymeric amide under the existence of ruthenium catalyst.
Background technology
Polymeric amide is normally prepared as the condensation reaction of acyl chlorides by diamines and diacid or two acid precursor.The business synthetic method of fatty polyamide generally includes following two steps: (1) is at room temperature first used in the diacid of 1:1 molar ratio and diamines and formed acid/alkali salt; (2) more described salt be heated to certain high temperature (for example, for polyamide 6,6 is 285 ° of C) and/or under high pressure by melt condensation, form polymeric amide.The main drawback of this class polycondensation method is harsh condition and/or produces Toxic waste (for example HCl).
In addition, polymeric amide also can be prepared by the ring-opening polymerization of lactan or N-carboxyamino acid anhydrides.For example, polyamide 6 is to commercially produce by ring-opening polymerization method.Yet, for the preparation of the cyclic monomer of ring-opening polymerization method, be still confined to harsh reaction conditions.
Recently, the people such as Milstein disclose and have used ruthenium catalyst to make alkohol and amine react to prepare the direct dehydrogenation amidation method of various acid amides in US2009/0112005A1, and molecular hydrogen is the unique by product in this reaction.With regard to high yield and high conversion and minimum by product generation aspect, this catalysis amidation method very advantageous.
The people such as Guan are at JACS (2011) 133, have reported that utilizing ruthenium catalyst catalytic dehydrogenation amidation method to prepare some main chain contains heteroatomic functionalized poly acid amides in the 1159th page.Described dehydrogenation polyamidation method is utilized the Ru catalyzer of 1 % by mole conventionally, by this Ru catalyzer and glycol and diamines at solvent system (for example, phenylmethylether, or phenylmethylether/DMSO (4:1) mixture) middle pre-mixing, then 120 ° of C heating 48 hours.By carefully selecting to be applicable to the glycol of heteroatoms replacement and/or the solvent system of diamines, dehydrogenation polyamidation method provides the functionalized poly acid amides of number-average molecular weight (Mn) within the scope of 10 to 30KDa.
Yet conventionally known fatty polyamide is as polyamide 6,6 and polymeric amide 10, the 10 optimum reaction condition preparation that can not use the people such as Guan to report, reason is that fatty polyamide only has low solubility in reported solvent system.In addition, the high catalyst load of 1 % by mole with respect to reactant has also improved the cost that carries out commercial production by dehydrogenation polyamidation method.
In view of fatty polyamide widespread use for parts and housing in automobile, Electrical and Electronic and textile industry, people expect that a kind of dehydrogenation polyamidation method of improvement can be used in synthetic fat family/aromatic polyamide.
The applicant finds beyond the consideration " solvent-free " in the situation that, under the existence of ruthenium catalyst, direct coupling glycol and diamines can be prepared fatty polyamide, polyamide 6 for example, 6 and polymeric amide 10,10 and non-fatty polyamide such as polyamide 6 T, polymeric amide 10T etc.Therefore, the invention provides new eco-friendly " solvent-free " dehydrogenation polyamidation method of preparing fatty polyamide, non-fatty polyamide and other functionalized poly acid amides.
Summary of the invention
The invention provides a kind of method of the polymeric amide for the preparation of formula 1,
Described method is included in the non-existent situation of solvent, and the glycol of formula 2 and the diamines of formula 3 are contacted with ruthenium catalyst;
Wherein:
A is-(CH
2)
p-W
q-(CH
2)
r-, wherein W is selected from C
3-C
8cycloalkyl, C
3-C
6the group of heterocyclic radical, aryl and heteroaryl, p is 1 to 8 integer, q be 0 or 1, r be 1 to 8 integer, and when q is 0, the summation of p and r is 2 to 14 integer;
B is-[(CH
2)
x-G-]
y-(CH
2)
z-, wherein G is selected from O, NH, C
3-C
8cycloalkyl, C
3-C
6the group of heterocyclic radical, aryl, alkaryl and heteroaryl, x is 0 to 4 integer, y is 0 to 4 integer; Z is 0 to 16 integer; When y is 0, z is 6 to 16 integer; And when y is not 0, z is 0 to 6 integer; And
N is 5 to 100 integer.
In an embodiment of the inventive method, wherein ruthenium catalyst is the compound of formula 4:
Wherein:
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
4cN) and isonitrile ((R
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, aralkyl, heterocyclic radical and heteroaryl.
Hereinafter method of the present invention will be described in further detail.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.When there is contradiction, with the definition in this specification sheets, be as the criterion.
Unless explicitly stated otherwise, trade mark indicates above.
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 that comprises listed key element, step, method, goods or device 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 of clearly not listing.
Conjunction " by ... form " 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.When phrase " by ... form " while appearing in the clause of claim main body rather than 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 ... form " 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 ... form " rank, position between " comprising " and " by ... composition ".
Term " solvent-free " or " not containing solvent " are used interchangeably in this article; It means in the methods of the invention, initial with during reaction in reaction, does not add solvent in the reaction mixture that contains glycol, diamines and Ru catalyzer.Gross weight meter based on reaction mixture, reaction mixture contains the solvent that is preferably less than 0.1 % by weight, is more preferably less than the solvent of 0.01 % by weight." solvent " refers to that organic solvent comprises toluene, phenylmethylether, DMSO etc.
Term " comprise " be intended to comprise by term " substantially by ... form " and " by ... composition " embodiment of comprising.Similarly, term " substantially by ... form " be intended to comprise by term " by ... form " embodiment that comprises.
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 being used separately or during as another group a part of, is referring to " C
1to C
16alkyl ", and refer to that linear and cladodification, saturated or unsaturated (for example thiazolinyl, alkynyl) group, unsaturated group are to be only applicable to carbonatoms in the alkyl situation while being 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 further by above-mentioned arbitrary substituting group, is replaced.As an example, " alkoxyalkyl " is the alkyl that alkoxy replaces.
Herein term " cycloalkyl " is used separately or during as another group a part of, refers to " C
3to C
8cycloalkyl " 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 or suberyl.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 " is used 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 " is used 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 " is used 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 for 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.
For the restriction of various groups and preferable range, be all 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 above.
During 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 the formed all scopes of arbitrary pairing that specifically disclose by any range limit or preferred value and any scope lower limit or preferred value, no matter and whether this scope discloses separately.For example, 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 and mark within the scope of this.
When 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 indication, "or" refers to the "or" of comprising property rather than the "or" of exclusiveness.For example, below any form A "or" B:A that all satisfies condition be that true (or existence) and B are pseudo-(or not existing), 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 " a kind of " before key element of the present invention or component and " one " are to the quantitative requirement of key element or component (being occurrence number) unrestriction.Therefore " one " or " a kind of " 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.
In specification sheets of the present invention and/or claims, term " homopolymer " refers to the polymkeric substance with single repeating unit; " multipolymer " refers to the polymkeric substance derived from two or more different repeat units.This analog copolymer can be random copolymers or segmented copolymer.
In describing fatty polyamide, when polymeric amide is while being formed by single lactam monomers ring-opening polymerization, it is named by the numeric suffix of the carbon number being provided by described monomer is provided.For example, PA 6 is prepared by hexanolactam.When fatty polyamide is while being prepared by the condensation of diamines and diacid, numeric suffix is provided by the carbon number being provided by monomer; Formerly, diacid is rear for diamines.For example, a kind of known polymeric amide PA 6,6, it refers to diamines (hexanediamine) and diacid (hexanodioic acid) 6 carbon atoms of polymer chain contribution of respectively doing for oneself.Be consistent with this naming rule, " PA 6,12 ", " nylon 6,12 " or " N 6,12 " in this article can Alternates, and it is the multipolymer of the diamines of 6 carbon and the diacid of 12 carbon.The limiting examples of other fatty polyamide comprises PA 4,6, PA 4,10, PA 5,10, PA 6,10, PA 6,11, PA 10,4, PA 10,5, PA 10,10, PA 10,12, PA 12,10, PA 12,12 etc.The example of polyamide copolymer comprises PA 6, and 6/PA 6; PA 6,6/PA 6/PA 12 etc.
The limiting examples of non-fatty polyamide comprises, aromatic polyamide is poly-(hexamethylene terephthalamide) (PA 6T), poly-(paraphenylene terephthalamide's decamethylene diamine) (PA 10T), poly-(sebacoyl Ursol D), poly-(terephthalylidene terephthalamide), poly-(terephthalylidene Isosorbide-5-Nitrae-subdamine), poly-(poly P phenylene diamine terephthalamide) (being p-polyaramide) and poly-(mpd-i) (being m-polyaramide) for example.
Embodiments of the present invention comprise:
Embodiment 1: describe the method for the polymeric amide of preparation formula 1 in summary of the invention, be included in the non-existent situation of solvent, the glycol of formula 2 and the diamines of formula 3 are contacted with ruthenium catalyst.
Embodiment 2: the method for embodiment 1, wherein ruthenium catalyst is the compound of the formula 4 described in summary of the invention.
Embodiment 3: the method for embodiment 2, wherein L
1p (R
1)
2.
Embodiment 4: the method for embodiment 3, wherein R
1it is the tertiary butyl.
Embodiment 5: the method for embodiment 2, wherein L
2n (R
3)
2.
Embodiment 6: the method for embodiment 5, wherein R
3it is ethyl.
Embodiment 7: the method for embodiment 2, wherein L
3cO.
Embodiment 8: the method for embodiment 1, wherein the glycol of the formula 2 of the scope of the amount of ruthenium catalyst with respect to every mole is approximately 0.01 % by mole to approximately 5 % by mole.
Embodiment 9: the method for embodiment 8, wherein the glycol of the formula 2 of the scope of the amount of ruthenium catalyst with respect to every mole is approximately 0.1 % by mole to approximately 1 % by mole.
Embodiment 10: the method for embodiment 9, wherein the glycol of the formula 2 of the scope of the amount of ruthenium catalyst with respect to every mole is approximately 0.2 % by mole to approximately 0.8 % by mole.
Embodiment 11: the method for embodiment 1, the mol ratio of the diamines of the glycol of its Chinese style 2 and formula 3 is approximately 0.9 to approximately 1.1.
Embodiment 12: the method for embodiment 11, the mol ratio of the diamines of the glycol of its Chinese style 2 and formula 3 is approximately 0.95 to approximately 1.05.
Embodiment 13: the method for embodiment 12, the mol ratio of the diamines of the glycol of its Chinese style 2 and formula 3 is approximately 0.99 to approximately 1.01.
Embodiment 14: the method for embodiment 1, the polymeric amide of its Chinese style 1 forms under noble gas atmosphere.
Embodiment 15: the method for embodiment 1, the polymeric amide of its Chinese style 1 is to form to the pressure of about 10bar at about 1bar.
Embodiment 16: the method for embodiment 15, the polymeric amide of its Chinese style 1 is to form to the pressure of about 5bar at about 1bar.
Embodiment 17: the method for embodiment 1, the polymeric amide of its Chinese style 1 is to form to the temperature range of approximately 300 ° of C at approximately 130 ℃.
Embodiment 18: the method for embodiment 17, the polymeric amide of its Chinese style 1 is to form to the temperature range of approximately 280 ° of C at approximately 140 ° of C.
Embodiment 19: the method for embodiment 1, the polymeric amide of its Chinese style 1 is fatty polyamide or non-fatty polyamide.
Embodiment 20: the method for embodiment 19, the polymeric amide of its Chinese style 1 is to be selected from polymeric amide 4,6, polymeric amide 4,10, polyamide 6,6, polyamide 6,10, polyamide 6,12, polymeric amide 10,4, polymeric amide 10,5, polymeric amide 10,10, the fatty polyamide of polymeric amide 12,10 and polymeric amide 12,12.
Embodiment 21: the method for embodiment 19, the polymeric amide of its Chinese style 1 is to be selected from poly-(hexamethylene terephthalamide) (PA 6T), poly-(paraphenylene terephthalamide's decamethylene diamine) (PA 10T), poly-(sebacoyl Ursol D), poly-(terephthalylidene terephthalamide) and poly-(terephthalylidene 1,4-subdamine) (poly (1,4-xylylenelene Isosorbide-5-Nitrae-piperazinediacetamide)) non-fatty polyamide.
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 the variable in embodiment is not only for method of the present invention and for polymeric amide prepared therefrom.
The present invention is by more detailed description hereinafter.
As shown in scheme 1, in the method for the invention, the polymeric amide of formula 1 in the situation that not there is not solvent by making the ruthenium catalyst of the glycol of formula 2 and the diamines of formula 3 and formula 4 contact prepared.
scheme 1
glycol
The glycol of multiple formula 2 can be used in method of the present invention, comprises that alkyl diol is (when A is-(CH
2)
p-W
q-(CH
2)
r-, q is 0, and p and r's and while being 2 to 14 integer); Cycloalkylalkyl glycol, heterocyclic radical alkyl diol, arylalkyl glycol and heteroarylalkyl glycol (when q is 1).
The example of suitable alkyl diol is BDO, 1,5-PD, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 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.
The example of cycloalkylalkyl glycol is 1,2-tetramethylene dimethanol, 1,3-pentamethylene dimethanol, 1,2-CHDM, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, two ring [2.2.1] heptane-2,3-dimethanol, two ring [2.2.2] octane-Isosorbide-5-Nitrae-dimethanols, two ring [2.2.2] octane-2,3-dimethanol or octahydro-4,7-endo-methylene group-1H-indenes-1,5-dimethanol (CAS 86282-89-5) or 5,7-dimethyl-tri-ring [3.3.1.1
3,7] decane-1,3-dimethanol (CAS 81657-00-3).
The example of heterocyclic radical alkyl-dimethyl alcohol is 2,3-oxyethane dimethanol, 2,3-oxyethane di-alcohol, 3,3-trimethylene oxide di-alcohol, Isosorbide-5-Nitrae-diox-2,5-di-alcohol, 2,5-furyl dimethyl carbinol, Isosorbide-5-Nitrae-piperazine di-alcohol (CAS 122-96-3), Isosorbide-5-Nitrae-piperidines di-alcohol, 1,4-dioxo spiro [4.4] nonane-6,9-dimethanol, tetrahydric thiapyran-2,6-dimethanol, 7-oxygen two ring [2.2.1] heptane-2,3-dimethanol, 1,4-diox-2,6-dimethanol, Isosorbide-5-Nitrae-diox-2,5-dimethanol or 2,5-diazabicyclo [2.2.1] heptane-2,5-di-alcohol.
The example of arylalkyl glycol is 1,4-xylyl alcohol (p-xylyl alcohol), 1,3-xylyl alcohol (m-xylyl alcohol), 1,2-xylyl alcohol (o-xylyl alcohol), 4-methoxyl group-1,3-xylyl alcohol, 2,5-dimethyl-Isosorbide-5-Nitrae-xylyl alcohol, 1,8-naphthalene-dimethanol or 2,6-naphthalene dimethanol.
The example of heteroarylalkyl glycol is 1-methyl isophthalic acid H-pyrroles-2,3-dimethanol, 1H-pyrroles-2,5-dimethanol, 1H-imidazoles-1,2-dimethanol, 1H-imidazoles-4,5-dimethanol, 3,4-thiophene dimethanol, 2,3-thiophene dimethanol, 2,5-thiophene dimethanol, 3,4-furans-dimethanol, 2,5-FDM, 2,5-furans di-alcohol, 1,2,5-oxadiazole-3,4-dimethanol, 1H-1,2,3-triazole-Isosorbide-5-Nitrae-di-alcohol, 2,4-thiazole dimethanol, 3,4-pyridine dimethanol, 2,3-pyridine dimethanol, 3,5-pyridine dimethanol, 2,6-pyridine dimethanol, 3,4-pyridine di-alcohol, 2,4-pyridine di-alcohol, 2,6-pyridine di-alcohol, 3-methyl-2,5-pyrazine di-alcohol, 6-ethyl-2,5-pyridine dimethanol, 6-(trifluoromethyl)-2,3-pyridine dimethanol, 2,4-furans-dimethanol, 1,2-bis-(methylol) pyrroles, 1-methyl-3,5-bis-(methylol) pyrazoles, 2,5-thiazole dimethanol, 3,5-bis-(methylol) pyrazoles, 1-(phenyl methyl)-1H-1,2,4-triazole-3,5-dimethanol, 3-methyl-2,6-pyrazine dimethanol, 1,2-bis-(methylol) benzoglyoxaline, 2,3-quinoline dimethanol, 2,4-quinoline dimethanol, or 2,3-cumarone dimethanol.
The mixture of above-mentioned glycol also can be in the present invention.
Preferred glycol is BDO, 1,5-PD, 1,6-hexylene glycol, decamethylene-glycol, 1,12-dodecanediol, 1,4 cyclohexane dimethanol, Isosorbide-5-Nitrae-piperazine di-alcohol or Isosorbide-5-Nitrae-xylyl alcohol.
In an embodiment of the invention, the glycol of formula 2 comprises BDO, 1,5-PD, 1,6-hexylene glycol, decamethylene-glycol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, Isosorbide-5-Nitrae-piperazine di-alcohol, Isosorbide-5-Nitrae-xylyl alcohol and their mixture.
diamines
The diamines of multiple formula 3 can be used in method of the present invention.Useful diamines is any organic diamine with two primary aminos, comprises that alkyl diamine is (when B is-[(CH
2)
x-G-]
y-(CH
2)
z-, y is 0, and z is while being 6 to 16 integer); With cycloalkyl diamines, cycloalkylalkyl diamines, heterocyclic radical diamines, heterocyclic radical alkyl diamine, aryl diamine, aralkyl diamines, heteroaryl diamines and heteroarylalkyl diamines (when y is not 0).
The limiting examples of suitable alkyl diamine comprises 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1，10-diaminodecane, 1,11-undecane diamines and 1,12-dodecane diamines.
Other limiting examples of diamines comprises cycloalkyl diamines, for example 1, and 3-diamino-cyclohexane, 1; 4-diamino-cyclohexane, 3,3'-diamino-dicyclohexyl methane, 4,4'-diamino-dicyclohexyl methane, 3; 3'-dimethyl-4,4'-diamino-dicyclohexyl methane; Cycloalkylalkyl diamines, for example Isosorbide-5-Nitrae-diamino methylcyclohexane, 3-amino methyl-3,5,5-trimethylcyclohexyl amine; Aryl diamine, for example mphenylenediamine and Ursol D; Aralkyl diamines, for example m-xylene diamine and p dimethylamine.
What can understand is also may use the mixture of above-mentioned diamines.Preferred diamines is 1,6-hexanediamine, 1，10-diaminodecane, 1,12-dodecane diamines, m-xylene diamine, p dimethylamine, mphenylenediamine or Ursol D.
In an embodiment of the invention, the diamines of formula 3 comprise 1,6-oneself-diamines, 1，10-diaminodecane, 1,12-dodecane diamines, m-xylene diamine, p dimethylamine, mphenylenediamine, Ursol D and their mixture.
ruthenium catalyst
Method of the present invention is by the ruthenium of formula 4 (Ru) complex catalysis, without alkali or acid cocatalyst.In a preferred embodiment, Ru catalyzer is by the compounds represented of formula 4a:
Each R wherein
1and R
3all the groups independently selected from alkyl, cycloalkyl, aryl, aralkyl, heterocyclic radical and heteroaryl.
In another embodiment, the compound of formula 4a, wherein R
1the tertiary butyl and R
3be ethyl by formula 4b compounds represented, its commercially available Strem Chemical Inc. that derives from.
What can understand is when 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 0.01 % 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 mol ratio of reaction
No matter how reactant mixes, and the mol ratio of the diamines of the glycol of formula 2 and formula 3 is conventionally approximately 0.9 to approximately 1.1, or approximately 0.95 to approximately 1.05, or approximately 0.99 to approximately 1.01 scope, or is approximately 1.0 (that is, being almost equimolar ratio).
the mode of mixing
The method of scheme 1 is normally the Ru catalyzer of the compound except formula 2 and 3 and formula 4, without any carrying out in the situation of solvent.
The not special order of the mixing of the diamines of the glycol of formula 2 and formula 3.For processing ease, first the reactant of solid form is joined in reaction vessel, then add another reactant of liquid form.Conventionally room temperature and noble gas as nitrogen or argon gas atmosphere under, Ru catalyzer is joined in the reaction mixture of diamines of the glycol that contains formula 2 and formula 3.
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 fixing noble gas to flow down and carries out, and the hydrogen generating in reaction process can be blown away to avoid accumulating in reaction vessel the hydrogen of high density.
Temperature of reaction has no particular limits, and condition is that the boiling point of its at least more lower boiling reactant (glycol or diamines) will low 10-20 ° C, to avoid mol ratio because the loss having compared with lower boiling reactant changes.The temperature of reaction mixture conventionally between approximately 130 ° of C between approximately 300 ° of C, conventionally between approximately 140 ° of C between approximately 280 ° of C.
Depend on batch scale and the temperature of reaction of using, the time that reaction is carried out can be determined aptly.
The product of formula 1 can be separated by standard technique known in the art.Due to the product of formula 1 solid normally at room temperature, they are generally easily the most separated by filtration method, optionally can then with one or more organic solvents, clean to remove unreacted glycol and/or diamines, are then dried.The method of scheme 1 is set forth by following embodiment 1-16.
Embodiment
Abbreviation " E " representative " embodiment ", " CE " representative " comparative example ", its numeral below is wherein prepared the numbering of the embodiment of polymeric amide.Embodiment all prepares in a similar manner and tests.Per-cent is for by weight, except as otherwise noted.
material
All glycol and diamines be all purchased from CTI, Sigma Aldrich, and Alfa Aesar or SCRC, and directly use, without being further purified.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
FTIR spectrum is used Nicolet NEXUS 5700 & Continuum Microscope spectrometers to obtain; Use rhombus ATR pattern; Detector: DTGS; Spectral range 4000 ~ 400cm
-1.
1bruker 400MHz Advance II spectrometer is used in the collection of H NMR frequency spectrum.The deuterated solvent using is DMSO-d
6.The report of chemical shift be take tetramethylsilane (TMS) displacement and is moved down the ppm of (downfiled), the report YiHzWei unit of coupling constant as benchmark; " s " means unimodal, and " d " means bimodal, and " t " means three peaks, and " q " is four peaks, and " m " means multimodal, and " dd " means bimodal bimodal, and " dt " means the bimodal of three peaks, and " br s " means wide unimodal, and " br m " means wide multimodal.
Thermogravimetric analysis (TGA) is carried out under drying nitrogen and air atmosphere with TA Q500 device.Temperature is warming up to 700 ° of C for all samples with 20 ° of speed of C/ minute gradually by 35 ° of C.Thermostability is passed through T
dwith reporting based on heavy % after original sample weight after heating cycle.T
dfor heat decomposition temperature, it is the temperature corresponding to the intersection point of the tangent line of the maximum weight loss of the initial experiment baseline extending and thermogravimetric analysis curve.
Limiting viscosity (IV) is measured with Ostwald viscometer, uses m-cresol to test as solvent and under 30 ° of C.Experimental data based on three measurement collections is calculated IV.The viscosity-average molecular weight of specimen by under show that formula calculates:
Wherein:
M
vit is viscosity-average molecular weight;
[η] is limiting viscosity, dL/g; And
K
-1/awith 1/a be the literature value from known polymeric amide.For example, for NYLON610, K
-1/a1.07 * 10
4and 1/ α is 1.04.
End group titration carries out determining the end amino group concentration of the solution of specimen in m-cresol with Metrohm 809Tirando device, by perchloric acid, the indication that sports by electrode potential quantizes for it.By the amino quantity of end, according to J.E.Waltz and G.B.Taylor, be published in Anal.Chem.1947,19 (7), the method for 448-450 page is calculated number-average molecular weight.
catalytic dehydrogenation legal system is for the general step of polymeric amide
Weigh diamines (being generally solid form) and ruthenium catalyst and be placed in 50 or 100mL round-bottomed flask, at N
2under atmosphere, in mixture, add glycol, the mol ratio of glycol and diamines remains 1:1.By on flask, connect nitrogen balloon or slowly nitrogen gas stream to reaction, provide nitrogen protection.
The mixture of reactant and catalyzer is heated to the temperature between 130 ℃ to 300 ℃.What react is to be accompanied by hydrogen produce and can observe by disengaging of bubble.The viscosity of reaction mixture also increases along with the generation of polyamide products, until stirrer stops stirring or gel occurs.Reaction mixture continued heating after 1-2 hour, was cooled to room temperature.
Produced curing mixture is broken into fritter, and by the washing with alcohol of about 10-20mL 1-2 time.In vacuum drying oven, at 80 ℃, remaining solid is dried to 5-24 hour and weighs, thereby calculate its thick productive rate.By FTIR,
1h NMR identifies separated product with TGA.When separated polymeric amide has suitable solvability, by intrinsic viscosity and the amino volumetry of end group, measure the molecular-weight average of polymeric amide.
Embodiments of the present invention are further defined in following embodiment.
embodiment 1: polyamide 6, the preparation of 6 (PA 6,6)
By 1,6-hexylene glycol (1.31g), the mixture of hexanediamine (1.29g) and Ru catalyzer (20mg) is placed in and is equipped with N
2in the reaction flask of balloon, and at 180 ℃, heat 9 hours.Weigh separated product (0.52g) and by the FTIR of its FTIR spectrum and known PA 6,6 is contrasted and is accredited as PA 6,6.
FTIR：3297,3075.8,1649.4,1558.2,1461.2,1371.4,1307.4,1123.2,729.4cm
-1。
1h NMR (DMSO-d
6, 400MHz) δ 1.25-1.54 (m, 12H ,-CH
2-), 1.87-2.44 (m, 4H ,-COCH
2-), 3.01-3.27 (m, 4H ,-N-CH
2-) and 8.12 (br.s, 2H ,-NH-).
TGA:T
dbe 416 ° of C and remaining be heavily 9.3%.
embodiment 2: polyamide 6, the preparation of 10 (PA 6,10)
By decamethylene-glycol (1.93g), the mixture of hexanediamine (1.29g) and Ru catalyzer (20mg) is placed in and is equipped with N
2in the reaction flask of balloon, and at 180 ℃, heat 5.5 hours.Weigh separated product (2.75g) and by the FTIR of its FTIR spectrum and known PA 6,10 is contrasted and is accredited as PA 6,10.
FTIR：3301.8,3063.1,2928.5,2854.7,1731.9,1634.6,1538.3,1472.5,1419.3,1363.3,1292.5,1241.4,1188.5,1062.0,1018.6,685.3,581.4,545.1cm
-1。
Viscosity-average molecular weight is about 3000g/ mole; The number-average molecular weight of titration measuring (Mn) is about 2300g/ mole.
TGA:T
dbe 441 ° of C and remaining be heavily 2.8%.
embodiment 3: polyamide 6, the preparation of 10 (PA 6,10)
By 1,10-decanediol (7.72g), the mixture of hexanediamine (5.15g) and Ru catalyzer (40mg) is placed in the reaction flask that is equipped with prolong and nitrogen gas stream, and mixture passes through mechanical stirring 8 hours at 180 ℃, then further at 240 ℃, reacts 2.5 hours.Weigh separated product (8.99g) and by the FTIR of its FTIR spectrum and known PA 6,10 is contrasted and is accredited as PA 6,10.
FTIR：3296.2,2925.0,2852.6,1733.8,1643.6,1547.8,1460.8,1367.8,1260.8,1174.7,1125.0,1014.2,965.5,722.7cm
-1。
TGA:T
dbe 437 ° of C and remaining be heavily 2.6%.
embodiment 4: polyamide 6, the preparation of 10 (PA 6,10)
By decamethylene-glycol (1.93g), the mixture of hexanediamine (1.29g) and Ru catalyzer (20mg) is placed in and is equipped with N
2in the reaction flask of balloon, and at 150 ℃, heat 17 hours.Weigh separated product (0.87g) and by the FTIR of its FTIR spectrum and known PA 6,10 is contrasted and is accredited as PA 6,10.
FTIR：3294.6,3077.3,2929.3,2854.0,1915.6,1734.3,1641.2,1551.6,1461.9,1368.5,1253.3,1175.7,1124.7,1060.5,966.6,868.1cm
-1。
TGA:T
dbe 442 ° of C and remaining be heavily 2.8%.
comparative example 1: polyamide 6 in dimethyl sulfoxide (DMSO), 10 preparation
By 1,10-decanediol (0.97g), hexanediamine (0.64g), dimethyl sulfoxide (DMSO) (DMSO, 5mL) be placed in the mixture of Ru catalyzer (10mg) reaction flask that is equipped with prolong and nitrogen gas stream, at 180 ℃, mixture stirred 21 hours.Do not isolate insoluble solid.
embodiment 5: the preparation of poly-(terephthalylidene Isosorbide-5-Nitrae-subdamine) (PA pXP)
By Isosorbide-5-Nitrae-bis-(2-hydroxyethyl) piperazines (0.97g), the mixture of p dimethylamine (0.75g) and Ru catalyzer (10mg) is placed in and is equipped with N
2in the reaction flask of balloon, and at 180 ℃, heat 7 hours.Weigh separated product (0.23g) and identify by FTIR and TGA.
FTIR：3351.9,3026.1,2853.3,1922.2,1806.9,1641.8,1512.1,1420.9,1377.3,1299.5,1214.4,1108.5,1018.5,828.5cm
-1。
TGA:T
dbe 352 ° of C and remaining be heavily 41.8%.
embodiment 6: the preparation of poly-(terephthalylidene terephthalamide) (PA pXT)
By Isosorbide-5-Nitrae-phenylene dimethanol (0.77g), the mixture of Isosorbide-5-Nitrae-p dimethylamine (0.75g) and Ru catalyzer (10mg) is placed in the reaction flask that prolong and nitrogen gas stream are housed, and at 180 ℃, mixture is stirred 6.5 hours.Weigh separated product (0.27g) and identify by FTIR and TGA.
FTIR：3623.9,3361.5,3053.3,2866.9,1925.9,1642.0,1671.7,1540.4,1512.7,1421.2,1378.9,1302.5,1221.4,1110.6,1019.2,835.9cm
-1。
TGA:T
dbe 345 ° of C and remaining be heavily 10%.
embodiment 7: the preparation of polymeric amide 10,10 (PA 10,10)
By decamethylene-glycol (1.93g), the mixture of 1,10-diamino decane (1.91g) and Ru catalyzer (20mg) is placed in and is equipped with N
2in the reaction flask of balloon, and at 180 ℃, heat 5.5 hours.Weigh separated product (0.95g) and identify by FTIR and TGA.FTIR spectrum between compare test sample and known PA 10,10, separated product is proved to be PA 10,10.
FTIR:3209.3 (broad peak), 2924.6,2852.1,1731.5,1639.5,1550.1,1518.7,1462.8,1368.5,1303.1,1173.2,885.7,721.9cm
-1.
TGA:T
dbe 447 ° of C and remaining be heavily 0.4%.
embodiment 8: the preparation of polymeric amide 12,12 (PA 12,12)
By 1,12-dodecanediol (2.24g), the mixture of 1,12-dodecane diamines (2.22g) and Ru catalyzer (20mg) is placed in and is equipped with N
2in the reaction flask of balloon, and at 180 ℃, heat 5.5 hours.Weigh separated product (2.30g) and identify by FTIR and TGA.
FTIR:3201.1 broad peak, 2919.4,2850.0,1733.9,1639.3,1548.5,1518.7,1465.7,1368.5,1137.0,1057.4,919.7,7212.0cm
-1.
TGA:T
dbe 446 ° of C and remaining be heavily 0.2%.
embodiment 9: the preparation of polymeric amide 12,10 (PA 12,10)
By decamethylene-glycol (1.93g), the mixture of 1,12-dodecyl diamines (2.22g) and Ru catalyzer (20mg) is placed in the reaction flask that is equipped with prolong and nitrogen gas stream, and stirs 2.5 hours at 230 ℃.Weigh separated product (3.02g) and identify by FTIR and TGA.FTIR spectrum between compare test sample and known PA 12,10, separated product is proved to be PA 12,10.
FTIR：3307.8,2921.5,2851.3,1735.3,1641.3,1540.8,1465.9,1368.2,1302.9,1237.3,1163.6,1125.8,720.7,581.0cm
-1。
TGA:T
dbe that 429 ° of C and Yu Chong are 1.1%.
embodiment 10: the preparation of polymeric amide 12,10 (PA 12,10)
By decamethylene-glycol (5.23g), the mixture of 1,12-dodecyl diamines (6.01g) and Ru catalyzer (2.7mg) is placed in the reaction flask that is equipped with prolong and nitrogen gas stream, and mixture is stirred 2.5 hours at 250 ℃.Weigh separated product (7.92g) and identify by FTIR and TGA.
FTIR：3309.1,2923.8,2851.8,1736.2,1667.7,1463.9,1369.9,1340.4,1262.6,1124.7,1061.8,804.5,720.9cm
-1。
TGA:T
dbe 427 ° of C and remaining be heavily 0.07%.
embodiment 11: the preparation of polymeric amide 10,4 (PA 10,4)
By BDO (2.03g), the mixture of the Milstein catalyzer of 1,10-diamino decane (3.89g) and 40.8mg is placed in the reaction flask that is equipped with prolong and nitrogen gas stream, and mixture is stirred 16 hours at 180 ℃.Crude product with washing with alcohol and in vacuum drying oven dried overnight under 50 ° of C.Weigh separated product (1.18g) and identify by FTIR and TGA.
FTIR：3306,3060.2,2923.5,2851.9,1631.5,1538.7,1469.8,1425.3,1346.8,1281.9,1209.8,1163.5,1088.9,945.7,721.9,684.4,547.7cm
-1。
TGA:T
dbe 290 ° of C and remaining be heavily 10.5%.
embodiment 12: the preparation of polymeric amide 10,5 (PA 10,5)
By 1,5-PD (1.99g), the mixture of the Ru catalyzer of 1,10-diamino decane (3.29g) and 34.5mg is placed in the reaction flask that is equipped with prolong and nitrogen gas stream, and mixture is stirred 16 hours at 180 ℃.Weigh separated product (0.46g) and identify by FTIR and TGA.
FTIR：3296.9,3063.0,2924.1,2851.9,1649.8,1554.9,1460.0,1368.6,1305.6,1123.6,876.7,807.1,720.2cm
-1。
TGA:T
dbe 403 ° of C and remaining be heavily 11.7%.
embodiment 13: the preparation of poly-(paraphenylene terephthalamide's decamethylene diamine) (PA 10T)
By Isosorbide-5-Nitrae-phenylene dimethanol (1.54g), the mixture of 1,10-diamino decane (1.91g) and Ru catalyzer (20.2mg) is placed in the reaction flask that is equipped with prolong and nitrogen gas stream, and mixture is stirred 9 hours at 180 ℃.Weigh separated product (0.69g) and identify by FTIR and TGA.
FTIR：3274.4,3085.6,2924.1,2850.7,1642.9,1546.2,1466.9,1372.6,1217.1,1153.1,960.7,830.1,723.1,528.5cm
-1。
TGA:T
dbe 412 ° of C and remaining be heavily 13.2%.
embodiment 14: polyamide 6, the preparation of 10 (PA 6,10)
By decamethylene-glycol (2.88g), the mixture of hexanediamine (1.92g) and Ru catalyzer (30mg) is placed in the reaction flask that is equipped with prolong and nitrogen gas stream, and by mixture mechanical stirring 10 hours at 180 ℃.Weigh separated product (4.55g) and identify by FTIR and TGA.
FTIR：3341.3,3077.4,2927.0,2853.9,1641.5,1564.4,1460.2,1361.3,1319.0,1055.8,880.1,820.9,724.5cm
-1。
TGA:T
dbe 436 ° of C and remaining be heavily 3.0%.
embodiment 15: polyamide 6, the preparation of 10 (PA 6,10)
By decamethylene-glycol (7.67g), the mixture of hexanediamine (5.11g) and Ru catalyzer (10mg) is placed in and is equipped with N
2in the reaction flask of balloon, and mixture is stirred 22 hours at 180 ℃.Weigh separated product (12.08g) and identify by FTIR and TGA.
FTIR：3339.0,3302.6,2926.4,2853.7,1640.8,1564.1,1459.9,1373.5,1053.7,881.2,821.5,724.7cm
-1。
TGA:T
dbe 432 ° of C and remaining be heavily 0.4%.
embodiment 16: the preparation of poly-sebacoyl Ursol D(PA pB, 10)
By decamethylene-glycol (0.965g), the mixture of Ursol D (0.60g) and Ru catalyzer (10mg) is placed in and is equipped with N
2in the reaction flask of balloon, and mixture is stirred 11 hours at 180 ℃.Weigh separated product (0.85g) and identify by FTIR and TGA.
FTIR：3308.8,2925.4,2852.7,1730.3,1658.2,1605.4,1518.5,1466.8,1404.2,1359.0,1303.3,1247.4,1175.2,961.3,824.6,722.8,517.9cm
-1。
TGA:T
dbe 427 ° of C and remaining be heavily 10.69%.
By method of the present invention (as shown in scheme 1) and step as described herein, prepared the polymeric amide of formula 1 and by comprising
1the multiple characterizing methods such as H NMR, FTIR and TGA are confirmed.
Table 1 has been summed up the reaction details according to each embodiment of the inventive method.For the ease of comparison comparative example 1, also list in wherein.
Table 1
Listed details from table 1, following content is obvious.
Embodiment 1-16 has proved that dehydrogenation polyamidation that method of the present invention is suitable for the glycol of various formulas 2 and the diamines of formula 3 is to prepare various polymeric amide.In addition, method of the present invention has no particular limits temperature of reaction, and it has crossed over a wide region (i.e. 250 ℃ from 150 ℃ of embodiment 4 to embodiment 10).Similarly conclusion also can obtain from its reaction times, and its scope was from 2.5 hours to 17 hours.Conventionally, the increase of reaction times along with temperature of reaction can be shortened, for example, and the contrast of embodiment 2 and embodiment 4.
Embodiment 4 and comparative example 1 are compared, and when there is no solvent, described dehydrogenation polyamidation method provides the polymeric amide of expectation.Therefore, solvent-free is an important factor of the inventive method.The meaning of noting " solvent-free " is not add solvent in starting raw material (being glycol 2, diamines 3, or Ru catalyzer 4) and/or reaction mixture.Yet, do not need the moisture that removes trace maybe may be present in the impurity of comprising in starting raw material " solvent ".
Embodiment 9 and embodiment 10 are compared, and effectively Ru catalyst cupport can be low to moderate 0.02 % by mole of the glycol of every mole of formula 2, and it, is reported in 133, the 1159 pages in JACS (2011) far below people such as Guan.
It should be noted that, embodiment 14 and embodiment 15 be with identical starting raw material, under 180 ° of C, except different Ru catalyst cupport (0.4 % by mole with 0.05 % by mole) has carried out polyamidation, reacts.The time of reacting by prolongation, has the embodiment 15 of less catalyzer to match in excellence or beauty in high yield (97.5%) % of embodiment 14, provides polyamide 6,10 (97.2%).
In a word, solvent-free processing procedure of the present invention is prepared and has very large business potential under low effective catalyst load for various aliphatics and non-fatty polyamide, and provides with respect to the more clean processing procedure of traditional polymeric amide method and 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 modification under spirit of the present invention and substitute 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 these improvement and be equal to all in the claims in defined the spirit and scope of the present invention.
Claims (12)
1. the preparation method of the polymeric amide of formula 1:
Described method is included in the non-existent situation of solvent, and the glycol of formula 2 and the diamines of formula 3 are contacted with ruthenium catalyst;
Wherein:
A is-(CH
2)
p-W
q-(CH
2)
r-, wherein W is selected from C
3-C
8cycloalkyl, C
3-C
6the group of heterocyclic radical, aryl and heteroaryl, p is 1 to 8 integer, q be 0 or 1, r be 1 to 8 integer, and when q is 0, the summation of p and r is 2 to 14 integer;
B is-[(CH
2)
x-G-]
y-(CH
2)
z-, wherein G is selected from O, NH, C
3-C
8cycloalkyl, C
3-C
6the group of heterocyclic radical, aryl, alkaryl and heteroaryl, x is 0 to 4 integer, and y is 0 to 4 integer, and z is 0 to 16 integer; When y is 0, z is 6 to 16 integer; And when y is not 0, z is 0 to 6 integer; And
N is 5 to 100 integer.
2. method according to claim 1, wherein said ruthenium catalyst is the compound of formula 4:
Wherein:
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
4cN) and isonitrile ((R
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, aralkyl, heterocyclic radical and heteroaryl.
3. method according to claim 2, wherein L
1p (R
1)
2, L
2n (R
3)
2, and L
3cO.
4. method according to claim 3, wherein R
1the tertiary butyl, and R
3it is ethyl.
5. method according to claim 1, the glycol of the formula 2 of the amount of wherein said ruthenium catalyst with respect to every mole is 0.01 % by mole to 5 % by mole.
6. method according to claim 1, the mol ratio of the diamines of the glycol of its Chinese style 2 and formula 3 is 0.9 to 1.1.
7. method according to claim 6, the mol ratio of the diamines of the glycol of its Chinese style 2 and formula 3 is 0.99 to 1.01.
8. method according to claim 1 wherein makes the glycol of formula 2 and the diamines of formula 3 contact with described ruthenium catalyst under noble gas atmosphere.
9. method according to claim 1, wherein, under the temperature range of 130 ° of C to 300 ° of C, makes the glycol of formula 2 and the diamines of formula 3 contact with described ruthenium catalyst.
10. method according to claim 1, the polymeric amide of its Chinese style 1 is fatty polyamide or non-fatty polyamide.
11. methods according to claim 10, the polymeric amide of its Chinese style 1 is to be selected from polymeric amide 4,6, polymeric amide 4,10, polyamide 6,6, polyamide 6,10, polyamide 6,12, polymeric amide 10,4, polymeric amide 10,5, polymeric amide 10,10, the fatty polyamide of polymeric amide 12,10 and polymeric amide 12,12.
12. methods according to claim 10, the polymeric amide of its Chinese style 1 is the non-fatty polyamide that is selected from poly-(hexamethylene terephthalamide), poly-(paraphenylene terephthalamide's decamethylene diamine), poly-(sebacoyl Ursol D), poly-(terephthalylidene terephthalamide) and poly-(terephthalylidene Isosorbide-5-Nitrae-subdamine).
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| JP2020117588A (en) * | 2019-01-22 | 2020-08-06 | 三菱瓦斯化学株式会社 | Polyamide resin, composition and molded article |
| JPWO2020152974A1 (en) * | 2019-01-22 | 2021-11-25 | 三菱瓦斯化学株式会社 | Polyamide resin, composition and molded product |
| US20220064377A1 (en) * | 2019-01-22 | 2022-03-03 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin, composition, and molded article |
| JP7188118B2 (en) | 2019-01-22 | 2022-12-13 | 三菱瓦斯化学株式会社 | Polyamide resins, compositions and molded articles |
| JP7363822B2 (en) | 2019-01-22 | 2023-10-18 | 三菱瓦斯化学株式会社 | Polyamide resins, compositions and molded products |
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