CN110248982A - The method for synthesizing (complete) perfluoroalkyl polyether-aminoderivative - Google Patents
The method for synthesizing (complete) perfluoroalkyl polyether-aminoderivative Download PDFInfo
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- CN110248982A CN110248982A CN201780083982.7A CN201780083982A CN110248982A CN 110248982 A CN110248982 A CN 110248982A CN 201780083982 A CN201780083982 A CN 201780083982A CN 110248982 A CN110248982 A CN 110248982A
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
- C08G65/3255—Ammonia
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
- C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
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Abstract
Provide a kind of method for synthesizing (complete) the perfluoroalkyl polyether polymer (PFPE) at the one or more end of the chain comprising at least one amino.
Description
Technical field
Gather the present invention relates to a kind of for synthesizing (complete) fluorine at the one or more end of the chain comprising at least one amino
The method of ether polymer (PFPE).
Background technique
(complete) perfluoroalkyl polyether polymer (PFPE) is widely known and is used as lubricant.Except other things, magnetic recording
The derivative of medium (MRM) industrial application (complete) perfluoroalkyl polyether polymer is used for lubricated magnetic disk.For the application, it is typically used in
Amino-containing (complete) perfluoroalkyl polyether polymer is wrapped at the one or more end of the chain.
Except other things, (International Business Machine Corporation (IBM) (the INTERNATIONAL BUSINESS of US 6083600
MACHINES CORPORATION)) it discloses and is suitable for depositing to lubricant on magnetosphere alloy film, the wherein lubricant packet
Containing amine stabilized perfluoropolyether polymer.As suitable perfluoropolyether polymer, refer to from Montedisons SPA
(Montedison) Z-DOL, the Z-DIAC of (Italian (IT)) and carry out arrogant King Company (Daikin) (Japanese (JP))
Demnum(R).However, it is stated that these polymer decompose in disk drive environment.Therefore, in order to make lubricant stable, these
Polymer can use amine end groups, such as secondary or tertiary amine end groups sealing end.Except other things, the conventional profit with hydroxy functionality
Lubrication prescription can be blocked with amine compounds.The perfluoro polyether derivant that amido replaces can be prepared in the following manner: make Z- first
DOL is reacted in the presence of suitable acid acceptor with sulphonyl acid anhydrides or sulfonic acid chloride to form the ester of Z-DOL；Then the ester is separated simultaneously
And solvent is removed by distillation；As further route, the diamines of the ester simple function or difunctionality handles and removes excess
Diamines.
US 6984759 (solvay sulexi company (SOLVAY SOLEXIS S.P.A.)) disclose for by using
Gaseous Hydrogen restores corresponding tool in the presence of the catalyst being made of Pd, Rh or Ru for being carried on solid metal fluoride
There is the perfluoropolyether of-CN end group to prepare with reactive terminal group (including notably-CH2NH2) perfluoropolyether side
Method.
The method of primary amine is synthesized for example in US by the inclusion of the amination of the starting material of at least one-OH group
8946463 (Evonik Degussa Corp. (EVONIK DEGUSSA GMBH)), (the BASF joint-stock company of US 20120232292
(BASF SE) (German (DE))) and the middle disclosure of US 20120232309 (BASF joint-stock company (Germany)).
However, all do not disclose or refer in above patent document can be from the macromolecular with high molecular weight, such as
(complete) perfluoroalkyl polyether polymer starts to carry out direct aminatin.In addition, above patent document is all there is no suggestion that when synthesis is from high score
When (complete) the fluorination macromolecular of son amount starts, high conversion and selectivity can be obtained.
Summary of the invention
Applicant noted that the method known in the art for being typically used in synthesis PFPE aminoderivative, such as
The method described in US 6083600 cited above, needs several steps, has high cost and low-conversion.In addition, same
The method that sample discloses in US 6984759 shows to be included that the polymer of-CN end group needs lacking for several synthesis steps
Point.
The applicant faces the method for the amine derivative for needing the synthesis perfluoropolyether polymer of seldom synthesis step
Needs, this method have highly selective (preferably at least 90% or even higher) and high conversion (preferably at least 70% or
It is even higher), while being easily and conveniently at industrial scale.
Unexpectedly, applicants have discovered that the aminoderivative of (complete) perfluoroalkyl polyether polymer can advantageously via from
The direct aminatin preparation that (poly-) alkoxylate (complete) perfluoroalkyl polyether polymer starts.
Therefore, in a first aspect, it includes that there are two (complete) perfluoroalkyl polyether chains of the end of the chain for tool that the present invention relates to a kind of for synthesizing
[chain (Rpf)] (poly-) alkoxylate (complete) perfluoroalkyl polyether polymer [polymer (PN)] method, the wherein at least one end of the chain has
Meet the chain [chain (R of following formulaN)]:
-CH(J1)CH(J2)-NR1R2
Wherein
J1And J2Each of independently selected from hydrogen atom；Linear or branched alkyl group chain comprising from 1 to 3 carbon atom, it is excellent
Select methyl；Or aryl, preferred phenyl；With the proviso that J1And J2At least one of be hydrogen atom；And
R1And R2Each of the linear or branched alkyl group chain independently selected from hydrogen atom or comprising from 1 to 6 carbon atom；
And the wherein chain (Rpf) and the chain (RN) via (poly-) alkoxylate chain [chain (RO)] link together；
It the described method comprises the following steps:
(a) make at least one (complete) perfluoroalkyl polyether polymer [polymer (POH)] and it is at least one with formula HNR1R2Compound
It reacts, wherein R1And R2Each of be same or different to each other, the straight chain selected from hydrogen atom or comprising from 1 to 6 carbon atom
Or branched alkyl chain；
Polymer (the POH) comprising tool, there are two (complete) perfluoroalkyl polyether chain [chain (R of the end of the chainpf)], wherein at least one end of the chain band
There is the chain [chain (R for meeting one of following formulaOH)]:
(ROH-I)-[CH2CH2O]j1- H,
(ROH-II)-[CH2CH(J)O]j2- H or
(ROH-III)-[CH(J)CH2O]j3- H,
Wherein
J is independently the alkyl or aryl of linear chain or branched chain, preferably methyl, ethyl or phenyl, and
Each of j1, j2 and j3 are independently from 1 to 50 integers；
In the presence of following item:
(i) catalyst [compound (C)] of at least one element based at least one the 8th or 9 races for belonging to the periodic table of elements；
(ii) at least one organic phosphorus compound [compound (P)] and
(iii) at least one solvent.
Specific embodiment
For the purpose of this specification and following claims:
In the use of the round parentheses of the symbol or digital ambient of identification type, such as in statement as having in " polymer (P) " etc.
The purpose for distinguishing the symbol or number more preferably with the remainder of the text, and therefore the round parentheses can also be by
It omits；
Acronym " PFPE " representative " (complete) perfluoroalkyl polyether " and when be used as nominal notional word when, be based on context intended to
Mean the form of singular or plural；
Term " (complete) perfluoroalkyl polyether " is intended to refer to complete or partial fluorinated polymer.
Preferably, the chain (Rpf) it is the chain with following formula:
-O-D-(CFX)z1-O(Rf)(CFX’)z2-D*-O-
Wherein
Z1 and z2 are same or different to each other, and are equal to or more than 1；
X and X ' is same or different to each other, and is-F or-CF3,
On condition that X and X ' are-F when z1 and/or z2 is greater than 1；
D and D* are same or different to each other, and are the alkylidene chain comprising from 1 to 6 and even more preferably from 1 to 3 carbon atom, institute
Alkyl chain is stated optionally to be replaced by least one perfluoroalkyl for including from 1 to 3 carbon atom；
(Rf) include R ° of repetitive unit, be preferably made from it, the repetitive unit is independently selected from the following group, and the group is by following
Item composition:
(i)-CFXO-, wherein X is F or CF3；
(ii)-CFXCFXO-, wherein X, identical or different at each occurrence, is F or CF3, with the proviso that at least one X be-
F；
(iii)-CF2CF2CW2O-, wherein each W is same or different to each other, it is F, Cl, H；
(iv)-CF2CF2CF2CF2O-；
(v)-(CF2) j-CFZ-O-, wherein j is from 0 to 3 integer and Z is with general formula-O-R(f-a)The group of-T, wherein
R(f-a)It is the fluorine polyoxy alkylidene chain comprising from 0 to 10 repetitive unit of quantity, the repetitive unit selects among the following terms
It selects :-CFXO- ,-CF2CFXO-、-CF2CF2CF2O-、-CF2CF2CF2CF2O-, wherein each X is independently F or CF3And T is
C1-C3Perfluoroalkyl.
It is highly preferred that z1 and z2 are same or different to each other, and it is from 1 to 10, even more preferably from 1 to 3.
It is highly preferred that D and D*, it is same or different to each other, is with formula-CH2-、-CH2CH2Or-CH (, CF3)-chain.
Preferably, chain (Rf) meet following formula:
(Rf-I)
-[(CFX1O)g1(CFX2CFX3O)g2(CF2CF2CF2O)g3(CF2CF2CF2CF2O)g4]-
Wherein
-X1Independently selected from-F and-CF3,
-X2、X3It is same or different to each other and at each occurrence, is independently-F ,-CF3, with the proviso that at least one X be-
F；
- g1, g2, g3 and g4 are same or different to each other, and are independently >=0 integers so that g1+g2+g3+g4 from 2 to 300,
It is preferred that in the range of from 2 to 100；If at least two in g1, g2, g3 and g4 are not zero, different repetitive units is overall
On along the chain statistical distribution.
It is highly preferred that chain (Rf) selected from the chain with following formula:
(Rf-IIA)-[(CF2CF2O)a1(CF2O)a2]-
Wherein:
- a1 and a2 is independently >=0 integer, make number average molecular weight be in 900 and 10, between 000, preferably in 900 and 5,
Between 000；Both a1 and a2 are preferably not zero, and wherein ratio a1/a2 is preferably incorporated between 0.1 and 10；
(Rf-IIB)-[(CF2CF2O)b1(CF2O)b2(CF(CF3)O)b3(CF2CF(CF3)O)b4]-
Wherein:
B1, b2, b3, b4 are independently >=0 integers, and making number average molecular weight is in 900 and 10, between 000, preferably 900
Between 5,000；Preferably b1 is 0, and b2, b3, b4 are > 0, and wherein ratio b4/ (b2+b3) is >=1；
(Rf-IIC)-[(CF2CF2O)c1(CF2O)c2(CF2(CF2)cwCF2O)c3]-
Wherein:
Cw=1 or 2；
C1, c2 and c3 are independently >=0 integers, and being chosen to number-average molecular weight is in 900 and 10, between 000, preferably
Between 900 and 5,000；Preferably c1, c2 and c3 are entirely > 0, and wherein ratio c3/ (C1+c2) is generally below 0.2；
(Rf-IID)-[(CF2CF(CF3)O)d]-
Wherein:
D is the integer of > 0, and making number average molecular weight is in 900 and 10, between 000, preferably between 900 and 5,000；
(Rf-IIE)-[(CF2CF2C(Hal*)2O)e1-(CF2CF2CH2O)e2-(CF2CF2CH(Hal*)O)e3]-
Wherein:
-Hal*, it is identical or different at each occurrence, it is the halogen selected from fluorine and chlorine atom, preferably fluorine atom；
- e1, e2 and e3 are same or different to each other, and are independently >=0 integers, so that the sum of (e1+e2+e3) is included in 2 and 300
Between.
It is more preferred still that chain (Rf) meet following formula (Rf- III):
(Rf-III)-[(CF2CF2O)a1(CF2O)a2]-
Wherein:
- a1 and a2 is the integer of > 0, make number average molecular weight be in 900 and 10, between 000, preferably in 900 and 5,000 it
Between, wherein ratio a1/a2 is commonly included between 0.1 and 10, more preferably between 0.2 and 5.
Preferably, the chain (RN) meet following formula (RN- I*) to (RNOne of-III*):
(RN-I*)-CH2CH2-NR1R2
(RN-II*)-CH2CH(CH3)-NR1R2
(RN-III*)-CH(CH3)CH2-NR1R2
Wherein
R1And R2It is as defined above.
It is highly preferred that chain (the RN) meet formula (R as indicatedN-I*)。
It is highly preferred that R1And R2The two is hydrogen atom.
Preferably, the chain (RO) meet following formula:
-[(CH(J)CH(J*)O]j-
Wherein
J is from 1 to 50, more preferably from 1 to 20, even more preferably from 1 to 10, even more preferably from from 1 to 8 integer；
Each of J and J* are independently selected from hydrogen atom；Linear or branched alkyl group chain comprising from 1 to 3 carbon atom, it is more excellent
Select methyl；Or aryl, more preferable phenyl；
With the proviso that at least one of J and J* are hydrogen atoms.
According to preferred embodiment, J and J* are independently selected from hydrogen atom and methyl.Even further preferably, J and J* are both
For hydrogen atom.
According to preferred embodiment, j is from 1 to 6 integer.
Comprising having the chain (R there are two the end of the chainpf) (wherein two end of the chain has chain (R as defined aboveN)) polymerization
Object (PN) embodiment be particularly preferred in the present invention.
According to another embodiment, polymer (PN) it include chain (Rpf), wherein only one of its end of the chain is with as defined above
Chain (RN) and another end of the chain have selected from the following terms group: halogen atom, preferably fluorine atom；Include from 1 to 6 carbon
The perfluorinated alkyl of atom, preferably-CF3、-C2F5、C3F7。
Preferably, the polymer (POH) it include chain (Rpf), which is as above for polymer (PN) define.
Preferably, the chain (ROH) meet following formula (ROH- I*) to (ROHOne of-III*):
(ROH-I*)-(CH2CH2O)j1-H
(ROH-II*)-[CH2CH(CH3)O]j2-H
(ROH-III*)-[(CH2CH2O)j3-(CH2CH(CH3)O)j4]j(x)-H
Wherein
J1 and j2 be each independently from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8 and
Even more preferably from from 1 to 6 integer；
J3, j4 and j (X) are greater than 1 integer so that the sum of j3 and j4 are from 2 to 15, more preferably from 3 to 15, even more preferably
From 4 to 15 and even more preferably from from 4 to 10；And
R1And R2It is as defined above.
It is highly preferred that chain (the ROH) meet formula (R as indicatedOH- I*), wherein j1 is from 1 to 6 integer.
Preferably, the polymer (POH) with the number between 400 and 10,000, more preferably between 400 and 5,000
Average molecular weight.
Preferred polymer (POH) can be by using reducing agent such as NaBH according to several method as known in the art4Change
It learns and restores corresponding PFPE carboxylic acid or ester or by as example in (the Ao Saimengte company of US 6509509
(AUSIMONTS.P.A.)) 7/5/2001, US 6573411 (Ao Saimengte company) 11/21/2002, WO 2008/122639
The catalytic hydrogenation manufacture disclosed in (solvay sulexi company) 10/16/2008.The precursor of PFPE carboxylic acid or PFPE ester can root
According to different methods, such as the oxidation polymerization by fluoroolefins or the ring-opening polymerisation by HFPO (hexafluoropropylene oxide) manufacture,
Such as in US 3847978 (Montedisons SPA (MONTEDISON S.P.A.)) 11/12/1974,3766251 (Meng Teai of US
Di Sheng company) 10/16/1973, US 3715378 (Montedisons SPA) 2/6/1973,3665041 (Montedison of US
Company) 5/23/1972, US 4647413 (Minnesota mining company (MINNESOTA MINING)) 3/3/1987,
EP151877 A (Minnesota mining company) 8/21/1985, US3442942 (Montedisons SPA) 5/6/1969, US
577291 (Ao Saimengte companies) 7/7/1998, US 5258110 (Ao Saimengte company (AUSIMONT S.R.L.)) 11/2/
It is taught in 1993 or US 7132574 (solvay sulexi company) 11/7/2006.
For example, the suitable polymer as starting material is extraordinary from Italian Su Wei in the method according to the invention
Polymer Company is with trade nameIt is commercially available.
Preferably, the compound (C) is based at least one element selected from the group below, which includes the following terms, preferably
Ground is made of the following terms: iron, cobalt, ruthenium, rhodium, osmium and iridium.It is highly preferred that the compound (C) is based on ruthenium.
Preferably, the compound (P) meets following formula (P-I):
Wherein
N is zero or 1；
Each of R1, R2, R3, R4, R5 and R6 are independently selected from the linear or branched alkyl group comprising from 1 to 10 carbon atom
Chain, wherein alkyl chain includes the alkyl diphenyl phosphine of from 1 to 4 carbon atom, comprising from 3 to 10 yuan of naphthenic base, comprising at least
One is selected from heteroatomic 3 yuan of N, O and S to 10 circle heterocyclic ring bases, and hetero atom of N, O and S are optionally selected from comprising at least one
5 yuan to 14 yuan aryl；The above group is optionally selected from fluorine atom, chlorine atom, bromine atom, hydroxyl, cyano ,-NH by one2With
The substituent group [group (S)] of linear or branched alkyl group chain comprising from 1 to 10 carbon atom replaces；
Y1、Y2And Y3It is σ key or selected from methylene, ethylidene, trimethylene, tetramethylene, pentamethylene or six each independently
The alkylidene of methylene, the alkylidene are optionally replaced by one or more groups (S) as defined above；
A is selected from optionally substituted N, O, P, C1-C6Alkyl is optionally selected from the heteroatomic C of N, O and S comprising one3-
C10Naphthenic base is optionally selected from the heteroatomic C of N, O and S comprising one5-C14The group of aromatic group；Or meet following formula
(A-I) and the group of one of (A-II):
(A-I)
(A-II)
Wherein
M and q is the integer of zero or from 1 to 4 each independently,
R8And R9It is each independently selected from the following group, which includes linear or branched alkyl group chain, fluorine comprising from 1 to 10 carbon atom
Atom, chlorine atom, bromine atom ,-OR7Group or-N (R7*)2Group, wherein R7And R7*It is each independently selected from hydrogen atom, includes
The linear or branched alkyl group chain of from 1 to 10 carbon atom and include 5 to 10 yuan of aryl；
X1And X2It is each independently selected from NH, O and S；
X3It is σ key or the bivalent group selected from following item :-N (R10)-、-O-、-S-、-C(R11)(R12)-, wherein R10Be comprising from
The linear or branched alkyl group chain of 1 to 10 carbon atom is selected from N, O and S comprising at least one comprising from 3 to 10 yuan of naphthenic base
Heteroatomic 3 yuan to 10 circle heterocyclic ring bases, heteroatomic 5 yuan to 14 yuan virtues of N, O and S are optionally selected from comprising at least one
Base；The above group is optionally replaced by one or more groups (S) as defined above；
R11And R12It is each independently selected from the linear or branched alkyl group comprising from 1 to 10 carbon atom, includes from 3 to 10 yuan
Naphthenic base, 3 yuan to 10 yuan cycloalkyloxies are selected from heteroatomic 3 yuan of N, O and S to 10 circle heterocyclic ring bases, optionally comprising at least one
Ground includes heteroatomic 5 yuan to the 14 yuan aryloxy group that at least one is selected from N, O and S；The above group is optionally one or more
Group (S) as defined above replaces.
It is highly preferred that the compound (P) meets formula (P-I) as indicated, in which:
N is zero or 1；
Each of R1, R2, R3, R4, R5 and R6 are independently selected from the linear or branched alkyl group comprising from 1 to 10 carbon atom
Chain includes from 3 to 10 yuan of naphthenic base, 5 yuan to 14 yuan aryl；
Y1、Y2And Y3It is σ key or the alkylidene selected from methylene, ethylidene and trimethylene each independently；
A is C1-C6Alkyl, C3-C10Naphthenic base or divalent or trivalent radical with following formula:
(A-II*)
Wherein
X2It is O；
X3Be σ key or have formula-C (R11)(R12)-bivalent group, wherein R11And R12It is each independently selected from comprising from 1 to 10
The linear or branched alkyl group of a carbon atom.
Even further preferably, the compound (P) is selected from the group, which includes the following terms, preferably by the following terms
Composition: 1,2- bis- (diphenylphosphino) ethane (diphos or dppe)；1,2- bis- (dicyclohexyl phosphino-) ethane；1,3- bis- (two
Phenyl phosphino-) propane (dppp)；Bis- (diphenylphosphino) butane (dppb) of Isosorbide-5-Nitrae-；2,3- bis- (dicyclohexyl phosphino-) ethane
(dcpe)；4,5- bis- (two-phenyl phosphino-s) -9,9- xanthphos (xantphos)；1,1 '-[2,7- bis- (1,1- dimethyl
Ethyl) -9,9- dimethyl -9H- xanthene -4,5- diyl] bis- (1,1 diphenyl) phosphino-s (t-bu-xantphos)；And 1,1,
1- tri- (diphenylphosphinomethyl) ethane (triphos).Xantphos is particularly preferred.
According to particularly preferred embodiment, according to the method for the present invention the step of (a) in the compound (C) and describedization
It is carried out in the presence of complex compound between conjunction object (P).Step (a) is carried out in the presence of comprising the complex compound of ruthenium and xantphos
Have been obtained for the unexpected result in terms of conversion ratio and selectivity.
According to preferred embodiment, the solvent is selected from polar solvent, nonpolar solvent and its mixture.
Preferably, the nonpolar solvent is selected from the group, which includes: saturated hydrocarbons and unsaturated hydrocarbons, such as hexane, heptan
Alkane, octane, hexamethylene, benzene,toluene,xylene and mesitylene；Linear or cyclic ether, such as tetrahydrofuran (THF), diethyl
Ether, Isosorbide-5-Nitrae-dioxanes, methyl tertiary butyl ether(MTBE) (MTBE), diethylene glycol dimethyl ether and 1,2- Ethyl Methyl Ether.
Preferably, the polar solvent is selected from the group, which includes polar protic and aprotic solvent.
Suitable polar non-solute is selected from the group, which includes dimethylformamide, formamide and acetonitrile.
It is highly preferred that the polar aprotic solvent is selected from water and alcohol.Suitable alcohol is selected from the group, which includes: 3,3- bis-
Methyl-1-butanol, 3,3- dimethyl -2- butanol, 2- trifluoromethyl -2- propyl alcohol, 2- methyl-2-propanol, 2- methyl -2- butanol,
2,3- dimethyl -2- butanol.
Good result is had been obtained for using at least one alcohol.
Preferably, step (a) is by by least one polymer (POH) at least one compound (C) and institute
It states at least one compound (P) and mixes progress.
Optionally, before carrying out step (a), step (a is carried out0), the step (a0) include will it is as defined above described in
At least one compound (C), at least one compound (P) and the solvent are mixed to provide mixture [mixing
Object (CP)], and then make the mixture (CP) and at least one polymer (P in step (a)OH) and described have
Formula HNR1R2Compound contact.
Preferably, the step (a0) under heating, more preferably from 50 DEG C to 200 DEG C, even more preferably from 100
DEG C to carrying out at a temperature of 180 DEG C.
Preferably, the step (a0) carried out under the pressure from about 1.5 to 3atm under stress, more preferably.
Preferably, the step (a0) carry out under an inert atmosphere, more preferred with or mixtures thereof argon gas, nitrogen.
Preferably, the compound (C) is to be based on the polymer (POH) total weight be higher than 0.01wt.%, more preferably
Amount from 0.05wt.% to 10wt.% and even more preferably from 0.1wt.% to 1.0wt.% uses.
Preferably, step (a) is by making at least one polymer (P as defined aboveOH) and it is at least one with formula
HNR1R2Compound react and carry out, wherein R1And R2Each of be same or different to each other, selected from hydrogen atom or comprising from
The linear or branched alkyl group chain of 1 to 3 carbon atom, with the proviso that R1And R2At least one of be hydrogen atom.According to preferred reality
Apply example, R1And R2Both hydrogen atoms.
Preferably, step (a) under heating, more preferably from 60 DEG C to 210 DEG C, even more preferably from 110 DEG C to
It is carried out at a temperature of 190 DEG C.
The present invention will be hereinafter illustrated in more details by means of the example being contained in following experimental part；These
Example is merely illustrative and is in no way to be construed as limiting of the scope of the present invention.
Experimental section
Materials and methods:
Polymer (I)-meets poly- (ethyoxyl) perfluoropolyether of following formula: HO (CH2CH2O)j1CH2CF2O(CF2CF2O)a1
(CF2O)a2CF2CH2(OCH2CH2)j1OH
Wherein j1=5, a1/a2 about 1, number-average molecular weight (Mn) 2,200 and F=1.8, are disclosed according in WO 2014/090649
Program manufacture.
Polymer (II)-meet following formulaE10H PFPE:HO (CH2CH2O)j1CH2CF2O
(CF2CF2O)a1(CF2O)a2CF2CH2O(CH2CH2O)j1H
With j1=1.79, a1/a2=1.2, number-average molecular weight (Mn) 1,765 and equivalent weight (Ew) 962.
The amination of example 1- polymer (I)
Under an argon, by carbonyl chlorine hydrogen three (triphenylphosphine) ruthenium (II) of 0.024g (0.025mmol) (No. CAS:
16971-33-8), the xantphos (No. CAS: 161265-03-8) and 8mL of 0.017g (0.030mmol) as solvent
2- methyl -2- butanol is placed in 30mL stainless steel autoclave (internal diameter 2.0em).Then by autoclave vacuum pump depletion, and
Then with 2 bars of argon pressurization.Then autoclave is heated at 140 DEG C, while stirred 1 hour.After cooling to room-temperature,
The polymer (I) of 2ml (3.0g) is added by autoclave opening and under an argon.Autoclave is closed and uses vacuum again
Pump depletion.Then by the NH of 1.0g3It is compressed in autoclave from gas cylinder, while the cooling autoclave in ice water.Then it is stirring
It is lower that mixture is heated at 160 DEG C and is maintained 12 hours at that same temperature.After cooling to room-temperature, by autoclave
It is slowly vented, reaction mixture is evaporated under reduced pressure on a rotary evaporator to remove solvent.Remaining liquid is filtered
It is used in combination13C-NMR analysis.
(remainder is for conversion ratio that analysis shows the 100% hydroxyl end of the chain and 95% selectivity to primary amine
Secondary amine as by-product).
The amination of example 2- polymer (II)
Identical program described in example 1 is repeated since polymer (II).
Pass through13The analysis of C-NMR shows the conversion ratio of the 92% hydroxyl end of the chain and 93% selectivity to primary amine
(remainder is the secondary amine as by-product).
The amination of example 3- polymer (I)
Since polymer (I) and use the CAS 16971-33-8 and 0.0087g of 0.012g (0.0125mmol)
The CAS 161265-03-8 of (0.015mmol) repeats identical program described in example 1.
Pass through13The analysis of C-NMR shows the conversion ratio of the 70% hydroxyl end of the chain and 94% selectivity to primary amine
(remainder is the secondary amine as by-product).
The amination of example 4- polymer (II)
Under an argon, by the CAS of CAS 16971-33-8 of 0.024g (0.025mmol), 0.017g (0.030mmol)
The polymer (II) of 161265-03-8,2ml (3.0g) and the 2- methyl -2- butanol as solvent of 8mL are placed in 30mL stainless steel
In autoclave, which is closed and with vacuum pump depletion.Then by the NH of 1.0g3It is compressed in autoclave from gas cylinder,
The cooling autoclave in ice water simultaneously.Then mixture is heated under stiring at 160 DEG C and is tieed up at that same temperature
It holds 12 hours.After cooling to room-temperature, autoclave is slowly vented, reaction mixture is being depressurized on a rotary evaporator
Lower evaporation is to remove solvent.Remaining liquid is filtered and is used in combination13C-NMR analysis.
Analysis show 85% the hydroxyl end of the chain conversion ratio and 92% to primary amine selectivity (remainder be make
For the secondary amine of by-product).
The amination of comparison example 1- polymer (II) in the absence of a solvent
Identical program described in example 2 is repeated, but without adding the 2- methyl -2- butanol as solvent.
Pass through13The analysis of C-NMR shows the conversion ratio of the 42% hydroxyl end of the chain and 77% selectivity to primary amine
(remainder is the secondary amine as by-product).
Claims (15)
1. one kind is for synthesizing the i.e. polymer (P of (poly-) alkoxylate (complete) perfluoroalkyl polyether polymerN) method, the polymer
(PN) comprising tool, there are two (complete) perfluoroalkyl polyether chain, that is, chain (R of the end of the chainpf), the wherein at least one end of the chain, which has, meets the chain of following formula i.e.
Chain (RN):
-CH(J1)CH(J2)-NR1R2
Wherein
J1And J2Each of independently selected from hydrogen atom；Linear or branched alkyl group chain comprising from 1 to 3 carbon atom, preferably
Methyl；Or aryl, preferred phenyl；With the proviso that J1And J2At least one of be hydrogen atom；And
R1And R2Each of the linear or branched alkyl group chain independently selected from hydrogen atom or comprising from 1 to 6 carbon atom；
And the wherein chain (Rpf) and the chain (RN) via (poly-) alkoxylate chain, that is, chain (RO) link together；
It the described method comprises the following steps:
(a) make at least one (complete) perfluoroalkyl polyether polymer i.e. polymer (POH) and it is at least one with formula HNR1R2Compound
It reacts, wherein R1And R2Each of be same or different to each other, the straight chain selected from hydrogen atom or comprising from 1 to 6 carbon atom
Or branched alkyl chain；
Polymer (the POH) comprising tool, there are two (complete) perfluoroalkyl polyether chain, that is, chain (R of the end of the chainpf), the wherein at least one end of the chain has
Meet the chain i.e. chain (R of one of following formulaOH):
(ROH-I) -[CH2CH2O]j1- H,
(ROH-II) -[CH2CH(J)O]j2- H or
(ROH-III) -[CH(J)CH2O]j3- H,
Wherein
J is independently the alkyl or aryl of linear chain or branched chain, preferably methyl, ethyl or phenyl, and
Each of j1, j2 and j3 are independently from 1 to 50 integers；
In the presence of following item:
(i) the catalyst i.e. compound (C) of at least one element based at least one the 8th or 9 races for belonging to the periodic table of elements；
(ii) at least one organic phosphorus compound, that is, compound (P) and
(iii) at least one solvent.
2. according to the method described in claim 1, wherein, the chain (Rpf) it is the chain for meeting following formula:
-O-D-(CFX)z1-O(Rf)(CFX’)z2-D*-O-
Wherein
Z1 and z2 are same or different to each other, and are equal to or more than 1；
X and X ' are same or different to each other, and are-F or-CF3,
On condition that X and X ' are-F when z1 and/or z2 is greater than 1；
D and D* are same or different to each other, and are the alkylidene chain comprising from 1 to 6 and even more preferably from 1 to 3 carbon atom, institute
Alkyl chain is stated optionally to be replaced by least one perfluoroalkyl for including from 1 to 3 carbon atom；
(Rf) it include repetitive unit Ro, be preferably made from it, the repetitive unit is independently selected from the following group, and the group is by following
Item composition:
(i)-CFXO-, wherein X is F or CF3；
(ii)-CFXCFXO-, wherein X, identical or different at each occurrence, is F or CF3, with the proviso that at least one X is-F；
(iii)-CF2CF2CW2O-, wherein each W is same or different to each other, it is F, Cl, H；
(iv)-CF2CF2CF2CF2O-；
(v)-(CF2)j- CFZ-O-, wherein j is from 0 to 3 integer and Z is with general formula-O-R(f-a)The group of-T, wherein
R(f-a)It is the fluorine polyoxy alkylidene chain comprising from 0 to 10 repetitive unit of quantity, the repetitive unit selects among the following terms
It selects :-CFXO- ,-CF2CFXO-、-CF2CF2CF2O-、-CF2CF2CF2CF2O-, wherein each X is independently F or CF3And T is
C1-C3Perfluoroalkyl.
3. according to the method described in claim 2, wherein, the chain (Rf) meet following formula:
(Rf-I)
-[(CFX1O)g1(CFX2CFX3O)g2(CF2CF2CF2O)g3(CF2CF2CF2CF2O)g4]-
Wherein
-X1Independently selected from-F and-CF3,
-X2、X3It is same or different to each other and at each occurrence, is independently-F ,-CF3, with the proviso that at least one X be-
F；
- g1, g2, g3 and g4 are same or different to each other, and are independently >=0 integers so that g1+g2+g3+g4 from 2 to 300,
It is preferred that in the range of from 2 to 100；If at least two in g1, g2, g3 and g4 are not zero, different repetitive units is overall
On along the chain statistical distribution.
4. the method according to any one of Claims 2 or 3, wherein the chain (Rf) it is selected from following formula:
(Rf-IIA) -[(CF2CF2O)a1(CF2O)a2]-
Wherein:
- a1 and a2 is independently >=0 integer, make number average molecular weight be in 900 and 10, between 000, preferably in 900 and 5,
Between 000；Both a1 and a2 are preferably not zero, and wherein ratio a1/a2 is preferably incorporated between 0.1 and 10；
(Rf-IIB) -[(CF2CF2O)b1(CF2O)b2(CF(CF3)O)b3(CF2CF(CF3)O)b4]-
Wherein:
B1, b2, b3, b4 are independently >=0 integers, and making number average molecular weight is in 900 and 10, between 000, preferably 900
Between 5,000；Preferably b1 is 0, and b2, b3, b4 are > 0, and wherein ratio b4/ (b2+b3) is >=1；
(Rf-IIC) -[(CF2CF2O)c1(CF2O)c2(CF2(CF2)cwCF2O)c3]-
Wherein:
Cw=1 or 2；
C1, c2 and c3 are independently >=0 integers, and being chosen to number-average molecular weight is in 900 and 10, between 000, preferably
Between 900 and 5,000；Preferably c1, c2 and c3 are entirely > 0, and wherein ratio c3/ (C1+c2) is generally below 0.2；
(Rf-IID) -[(CF2CF(CF3)O)d]-
Wherein:
D is the integer of > 0, and making number average molecular weight is in 900 and 10, between 000, preferably between 900 and 5,000；
(Rf-IIE)-[(CF2CF2C(Hal*)2O)e1-(CF2CF2CH2O)e2-(CF2CF2CH(Hal*)O)e3]-
Wherein:
-Hal*, it is identical or different at each occurrence, it is the halogen selected from fluorine and chlorine atom, preferably fluorine atom；
- e1, e2 and e3 are same or different to each other, and are independently >=0 integers, so that the sum of (e1+e2+e3) is included in 2 and 300
Between.
5. method according to any one of claim 2 to 4, wherein the chain (Rf) meet following formula (Rf- III):
(Rf-III) -[(CF2CF2O)a1(CF2O)a2]-
Wherein:
- a1 and a2 is the integer of > 0, make number average molecular weight be in 900 and 10, between 000, preferably in 900 and 5,000 it
Between, wherein ratio a1/a2 is commonly included between 0.1 and 10, more preferably between 0.2 and 5.
6. according to the method described in claim 1, wherein, the chain (RN) meet following formula (RN- I*) to (RNOne of-III*):
(RN-I*) -CH2CH2-NR1R2
(RN-II*) -CH2CH(CH3)-NR1R2
(RN-III*) -CH(CH3)CH2-NR1R2
Wherein
R1And R2Each of the linear or branched alkyl group chain independently selected from hydrogen atom or comprising from 1 to 6 carbon atom.
7. according to the method described in claim 1, wherein, the chain (RO) meet following formula:
-[(CH(J)CH(J*)O]j-
Wherein
J is from 1 to 50, more preferably from 1 to 20, even more preferably from 1 to 10, even more preferably from from 1 to 8 integer；
Each of J and J* are independently selected from hydrogen atom；Linear or branched alkyl group chain comprising from 1 to 3 carbon atom, it is more excellent
Select methyl；Or aryl, more preferable phenyl；
With the proviso that at least one of J and J* are hydrogen atoms.
8. according to the method described in claim 1, wherein, the chain (ROH) meet following formula (ROH- I*) to (ROHOne of-III*):
(ROH-I*) -(CH2CH2O)j1-H
(ROH-II*) -[CH2CH(CH3)O]j2-H
(ROH-III*) -[(CH2CH2O)j3-(CH2CH(CH3)O)j4]j(X)-H
Wherein
J1 and j2 be each independently from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10, even more preferably from 1 to 8 and
Even more preferably from from 1 to 6 integer；
J3, j4 and j (X) are greater than 1 integer so that the sum of j3 and j4 are from 2 to 15, more preferably from 3 to 15, even more preferably
From 4 to 15 and even more preferably from from 4 to 10；And
R1And R2Each of the linear or branched alkyl group chain independently selected from hydrogen atom or comprising from 1 to 6 carbon atom.
9. being somebody's turn to do according to the method described in claim 1, wherein, the compound (C) is based at least one element selected from the group below
Group is formed including the following terms, preferably by the following terms: iron, cobalt, ruthenium, rhodium, osmium and iridium.
10. according to the method described in claim 1, wherein, the compound (P) meets following formula (P-I):
Wherein
N is zero or 1；
Each of R1, R2, R3, R4, R5 and R6 are independently selected from the linear or branched alkyl group comprising from 1 to 10 carbon atom
Chain, wherein alkyl chain includes the alkyl diphenyl phosphine of from 1 to 4 carbon atom, comprising from 3 to 10 yuan of naphthenic base, comprising at least
One is selected from heteroatomic 3 yuan of N, O and S to 10 circle heterocyclic ring bases, and hetero atom of N, O and S are optionally selected from comprising at least one
5 yuan to 14 yuan aryl；The above group is optionally selected from fluorine atom, chlorine atom, bromine atom, hydroxyl, cyano ,-NH by one2With
Substituent group, that is, group (S) of linear or branched alkyl group chain comprising from 1 to 10 carbon atom replaces；
Y1、Y2And Y3It is σ key or selected from methylene, ethylidene, trimethylene, tetramethylene, pentamethylene or six each independently
The alkylidene of methylene, the alkylidene are optionally replaced by one or more groups (S) as defined above；
A is selected from optionally substituted N, O, P, C1-C6Alkyl is optionally selected from the heteroatomic C of N, O and S comprising one3-C10
Naphthenic base is optionally selected from the heteroatomic C of N, O and S comprising one5-C14The group of aromatic group；Or meet following formula
(A-I) and the group of one of (A-II):
(A-I)
(A-II)
Wherein
M and q is the integer of zero or from 1 to 4 each independently,
R8And R9It is each independently selected from the following group, which includes linear or branched alkyl group chain, fluorine comprising from 1 to 10 carbon atom
Atom, chlorine atom, bromine atom ,-OR7Group or-N (R7*)2Group, wherein R7And R7*It is each independently selected from hydrogen atom, includes
The linear or branched alkyl group chain of from 1 to 10 carbon atom and include 5 to 10 yuan of aryl；
X1And X2It is each independently selected from NH, O and S；
X3It is σ key or the bivalent group selected from following item :-N (R10)-、-O-、-S-、-C(R11)(R12)-, wherein R10Be comprising from
The linear or branched alkyl group chain of 1 to 10 carbon atom is selected from N, O and S comprising at least one comprising from 3 to 10 yuan of naphthenic base
Heteroatomic 3 yuan to 10 circle heterocyclic ring bases, heteroatomic 5 yuan to 14 yuan virtues of N, O and S are optionally selected from comprising at least one
Base；The above group is optionally replaced by one or more groups (S) as defined above；
R11And R12It is each independently selected from the linear or branched alkyl group comprising from 1 to 10 carbon atom, includes from 3 to 10 yuan of ring
Alkyl, 3 yuan to 10 yuan cycloalkyloxies are selected from heteroatomic 3 yuan of N, O and S to 10 circle heterocyclic ring bases, optionally comprising at least one
Heteroatomic 5 yuan to the 14 yuan aryloxy group of N, O and S are selected from comprising at least one；The above group optionally by it is one or more such as
Group (S) defined above replaces.
11. according to the method described in claim 10, wherein, compound (P) meeting formula (P-I)
Wherein:
N is zero or 1；
Each of R1, R2, R3, R4, R5 and R6 are independently selected from the linear or branched alkyl group comprising from 1 to 10 carbon atom
Chain includes from 3 to 10 yuan of naphthenic base, 5 yuan to 14 yuan aryl；
Y1、Y2And Y3It is σ key or the alkylidene selected from methylene, ethylidene and trimethylene each independently；
A is C1-C6Alkyl, C3-C10Naphthenic base or divalent or trivalent radical with following formula:
(A-II*)
Wherein
X2It is O；
X3Be σ key or have formula-C (R11)(R12)-bivalent group, wherein R11And R12It is each independently selected from comprising from 1 to 10
The linear or branched alkyl group of a carbon atom.
12. according to particularly preferred embodiment, according to the method for the present invention the step of (a) in the compound (C) and describedization
It is carried out in the presence of complex compound between conjunction object (P).
13. according to the method described in claim 1, wherein, the solvent is polar aprotic solvent.
14. according to the method described in claim 1, wherein, before carrying out step (a), carrying out step (a0), the step (a0)
Including will be according to claim 1 at least one compound (C), at least one chemical combination defined in any one of 13
Object (P) and the solvent are mixed to provide mixture i.e. mixture (CP), and are then made in step (a) described mixed
Close object (CP) and at least one polymer (POH) and it is described with formula HNR1R2Compound contact.
15. according to the method described in claim 1, wherein, the compound (C) is based on the polymer (POH) gross weight
Amount is higher than the amount of 0.01wt.%.
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| US6083600A (en) * | 1998-03-10 | 2000-07-04 | International Business Machines Corporation | Stabilized perfluoropolyether lubricant |
| EP1388556A2 (en) * | 2002-08-01 | 2004-02-11 | Solvay Solexis S.p.A. | Proces for the preparation of perfluoropolyethers having aldehyde alcohol, amine end groups by catalytic reduction |
| US20100121106A1 (en) * | 2007-04-10 | 2010-05-13 | Solvay Solexis S.P.A. | Method for preparing carbonylic perfluoropolyethers |
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| US8785693B2 (en) * | 2011-03-08 | 2014-07-22 | Basf Se | Process for the preparation of primary amines by homogeneously catalyzed alcohol amination |
| WO2012119927A1 (en) * | 2011-03-08 | 2012-09-13 | Basf Se | Method for producing primary amines obtained by homogeneously catalyzed alcohol amination |
| JP2016006704A (en) * | 2014-06-20 | 2016-01-14 | デクセリアルズ株式会社 | Lubricant for magnetic recording medium and magnetic recording medium |
| US10723839B2 (en) * | 2015-07-09 | 2020-07-28 | Solvay Specialty Polymers Italy S.P.A. | Process for the synthesis of (per)fluoropolyether amines |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6083600A (en) * | 1998-03-10 | 2000-07-04 | International Business Machines Corporation | Stabilized perfluoropolyether lubricant |
| EP1388556A2 (en) * | 2002-08-01 | 2004-02-11 | Solvay Solexis S.p.A. | Proces for the preparation of perfluoropolyethers having aldehyde alcohol, amine end groups by catalytic reduction |
| US20100121106A1 (en) * | 2007-04-10 | 2010-05-13 | Solvay Solexis S.P.A. | Method for preparing carbonylic perfluoropolyethers |
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