CA2175151A1 - Di-carboxy terminated oligomer and bisimidazoline addition polymers and copolymers and process for obtaining them - Google Patents
Di-carboxy terminated oligomer and bisimidazoline addition polymers and copolymers and process for obtaining themInfo
- Publication number
- CA2175151A1 CA2175151A1 CA002175151A CA2175151A CA2175151A1 CA 2175151 A1 CA2175151 A1 CA 2175151A1 CA 002175151 A CA002175151 A CA 002175151A CA 2175151 A CA2175151 A CA 2175151A CA 2175151 A1 CA2175151 A1 CA 2175151A1
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- polymers
- formula
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- reaction
- oligomer
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
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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
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33317—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group heterocyclic
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
Abstract
Polymers and copolymers are provided comprising at least one recurring unit of formula:
in which R is a single bond, a linear hydrocarbon chain; R' is an aliphatic or aromatic hydrocarbon chain, which may be substituted, and of which the shortes chain linking the two neighboring --NH-- units carries two or three carbon atoms, and is the moiety of an ologomer of formula:
in which R is a single bond, a linear hydrocarbon chain; R' is an aliphatic or aromatic hydrocarbon chain, which may be substituted, and of which the shortes chain linking the two neighboring --NH-- units carries two or three carbon atoms, and is the moiety of an ologomer of formula:
Description
2 1 7 51 ~ 1 Dl-CARBOXY TERMINATED OLIGOMER AND BISIMIDAZOLINE ADDITION
POLYMERS AND COPOLYMERS AND PROCESS FOR OBTAINING THEM
BACKGROUND OF THE INVENTION
The present invention relates to polymers and copolymers able to attain high molecular weights and to a process for obtaining them at atmospheric pressure, without elimination of by-products, using a fast reaction that can be adapted to the RIM (reaction injection molding) process at 1 50-350C. More precisely, this reaction involves addition of bisimidazoline type chain couplers and carboxy reactive terminal oligomers.
Conventional poly-condensation reactions are equilibrium reactions. It is difficult to obtain high molecular weight polymers without operating at elevated temperature, under reduced pressure for a very long reaction time, with the risk of secondary reactions and, possibly, deterioration of the polymers.
To overcome these difficulties, the applicant has carried out bulk reaction of well-defined reactive terminal oligomers, at a temperature higher than their melting point, with molecules known as chain couplers (CC) in 20 order to obtain a product of high molecular weight. The chain couplers in which the applicant is interested are more precisely the bisimidazolines.
The use of chain couplers for increasing the molecular weight of polymers that are already of high molecular weight, carrying reactive functions, but present in small amounts, is already known. The viscosity of these polymers is then increased, and residual acidity decreased.
Thus, Japanese patent (Kokai) Tokkyo Koho JP 63 099,228 discloses coextrusion of a high molecular mass poly(ethylene terephtalate) carrying a small number of terminal carboxy functions, with a bisoxazoline.
However, this patent in which the starting materials are high 30 molecular mass polymers, does not indicate how to overcome the problems of obtaining such polymers, in particular by polycondensation. Additionally, that patent does not teach the use of bisimidazolines.
European patent applications in the name of the applicant disclose reactions between reactive terminal oligomers and bisoxazolines or bisoxazines (European Patent Application serial No. 93 401,873.0 of September 21, 1993) or bisoaxolones or bisoxazinones (European Patent Application serial No. 93 401,872.2 of September 21, 1993).
The value of using bisimidazolines under the same conditions is that they lead, after coupling, to the existence of linkages between P moieties only containing amide functions, as the recurring pattern demonstrates.
SUMMARY OF THE INVENTION
The present invention thus provides polymers and copolymers comprising at least one recurring unit of formula:
--NH--C---P--C--NH--R'--NH--C--R--C--NH--R' O O O O
in which:
R is a single bond, a linear hydrocarbon chain R' is an aliphatic or aromatic hydrocarbon chain, which may be substituted, and of which the shortest chain linking the two neighboring --NH-- units carries two or three carbon atoms, and --c--P--c--Il 11 is the moiety of an ologomer of formula:
H O--C--P--C--OH
Il 11 O O
R may for example be:
- a single bond - a (CH2)q type hydrocarbon chain where q is comprised between 1 and 24 in which one or several carbon atoms can be mono- or di-substituted and which may include an aliphatic or aromatic ring or an olefinic unsaturation, - an ortho-, meta- or para-phenylene or an ortho-, meta- or para-alkylphenylene which may be substituted.
R' can, for example, consist of:
- a-(CH2)p-, type hydrocarbon chain in which p = 2 or 3 of which one or several of the carbon atoms constituting it can be mono- or di-substituted by alkyl groups such as methyl, ethyl, propyl, - two of these consecutive carbon atoms additionally being able to be part of a benzene ring which may itself be substituted by one or several alkyl groups .
--C--P--C--Il 11 o o is the residue of a mono- or poly-block oligomer of formula:
H O--C--P--C--OH
Il 11 O O
the units of which can for example consist of polyamide, polyether, polyester.
This oligomer can be, in particular:
a) a di-COOH terminal polyamide of formula:
HO[ICl R2 --NH] lCI--R1--C [NH R2 --ICl 1 OH
O O
in which:
R2 is:
- a hydrocarbon chain constituting a lactame and/or an aminoacid, or - the structure --R ~ C--N H--R
POLYMERS AND COPOLYMERS AND PROCESS FOR OBTAINING THEM
BACKGROUND OF THE INVENTION
The present invention relates to polymers and copolymers able to attain high molecular weights and to a process for obtaining them at atmospheric pressure, without elimination of by-products, using a fast reaction that can be adapted to the RIM (reaction injection molding) process at 1 50-350C. More precisely, this reaction involves addition of bisimidazoline type chain couplers and carboxy reactive terminal oligomers.
Conventional poly-condensation reactions are equilibrium reactions. It is difficult to obtain high molecular weight polymers without operating at elevated temperature, under reduced pressure for a very long reaction time, with the risk of secondary reactions and, possibly, deterioration of the polymers.
To overcome these difficulties, the applicant has carried out bulk reaction of well-defined reactive terminal oligomers, at a temperature higher than their melting point, with molecules known as chain couplers (CC) in 20 order to obtain a product of high molecular weight. The chain couplers in which the applicant is interested are more precisely the bisimidazolines.
The use of chain couplers for increasing the molecular weight of polymers that are already of high molecular weight, carrying reactive functions, but present in small amounts, is already known. The viscosity of these polymers is then increased, and residual acidity decreased.
Thus, Japanese patent (Kokai) Tokkyo Koho JP 63 099,228 discloses coextrusion of a high molecular mass poly(ethylene terephtalate) carrying a small number of terminal carboxy functions, with a bisoxazoline.
However, this patent in which the starting materials are high 30 molecular mass polymers, does not indicate how to overcome the problems of obtaining such polymers, in particular by polycondensation. Additionally, that patent does not teach the use of bisimidazolines.
European patent applications in the name of the applicant disclose reactions between reactive terminal oligomers and bisoxazolines or bisoxazines (European Patent Application serial No. 93 401,873.0 of September 21, 1993) or bisoaxolones or bisoxazinones (European Patent Application serial No. 93 401,872.2 of September 21, 1993).
The value of using bisimidazolines under the same conditions is that they lead, after coupling, to the existence of linkages between P moieties only containing amide functions, as the recurring pattern demonstrates.
SUMMARY OF THE INVENTION
The present invention thus provides polymers and copolymers comprising at least one recurring unit of formula:
--NH--C---P--C--NH--R'--NH--C--R--C--NH--R' O O O O
in which:
R is a single bond, a linear hydrocarbon chain R' is an aliphatic or aromatic hydrocarbon chain, which may be substituted, and of which the shortest chain linking the two neighboring --NH-- units carries two or three carbon atoms, and --c--P--c--Il 11 is the moiety of an ologomer of formula:
H O--C--P--C--OH
Il 11 O O
R may for example be:
- a single bond - a (CH2)q type hydrocarbon chain where q is comprised between 1 and 24 in which one or several carbon atoms can be mono- or di-substituted and which may include an aliphatic or aromatic ring or an olefinic unsaturation, - an ortho-, meta- or para-phenylene or an ortho-, meta- or para-alkylphenylene which may be substituted.
R' can, for example, consist of:
- a-(CH2)p-, type hydrocarbon chain in which p = 2 or 3 of which one or several of the carbon atoms constituting it can be mono- or di-substituted by alkyl groups such as methyl, ethyl, propyl, - two of these consecutive carbon atoms additionally being able to be part of a benzene ring which may itself be substituted by one or several alkyl groups .
--C--P--C--Il 11 o o is the residue of a mono- or poly-block oligomer of formula:
H O--C--P--C--OH
Il 11 O O
the units of which can for example consist of polyamide, polyether, polyester.
This oligomer can be, in particular:
a) a di-COOH terminal polyamide of formula:
HO[ICl R2 --NH] lCI--R1--C [NH R2 --ICl 1 OH
O O
in which:
R2 is:
- a hydrocarbon chain constituting a lactame and/or an aminoacid, or - the structure --R ~ C--N H--R
o in which R3 and R4 are, respectively, the hydrocarbon moieties of a di-acid and of a diamine;
Rl represents the moiety of the organic di-acid employed as a chain terminator;
x and y are integers 2 0 such that x + y 2 1.
Such a polyamide can be obtained from:
- a lactame of formula co and/or aminoacid of formula H2N--R2--COOH and diamine H2N--R4--NH2, in the presence of an excess of di-acid of formula HOOC--R3--COOH .
The lactames of formula:
2l l5~51 NH
R/ I
2~co are for exmple C5 - C14 lactames such as caprolactames, dodecalactames .
The aminoacids of formula H2N--R2~OOH are for example aliphatic C5 - C24 aminoacids such as 11-amino-undecanoic acid.
The diacids of formula HOOC--Rl--COOH and HOOC--R3--COOH:
- aromatic di-acids, for example iso and terephtalic acids, dicarboxylic (in position 2,6; 1,5 ;2,7) naphtalene acids, 4,4'-dicarboxydiphenylether, 4,4'-dicarboxybiphenyl acids, - aliphatic diacids or anhydrides, for example which are for example branched or straight-chain C4 to C24 acids such as adipic, sebacic, decane-1,10-dioic, 1-dodecane, 12- dioic, fumaric acids, maleic anhydride, - cycloaliphatic di-acids such as cyclohexane-1,4-dicarboxylic acid.
The diamines of formula H2N--R4--NH2 can be:
- cycloaliphatic diamines, for example optionally methane-substituted 4,4'-diamino-dicyclohexyl such as bis (4-amino-3-methylcyclohexyl) methane, isophorone diamine, - aliphatic diamines, for example branched or straight chain C4 to C24 diamines, such as 1 ,6-hexamethylene-diamine, 1 ,1 2-dodecamethylene-20 diamine.
Examples of such oligomers are disclosed in EP-A-0,281,461 and EP-A-0,31 3,436.
b) a polyester with di-COOH terminations having an aliphatic or semi-aromatic structure that may be mono- or poly-olefinically unsaturated, obtained from excess di-acid and/or acid anhydride, such as succinic or phtalic anhydride, and those cited above, and diol, such as C2 to C24 linear or branched aliphatic diol, for example ethylene glycol, propylene glycol, 1,4-butane-dio-l, 1-5-pentane-diol, 1,6-hexane-diol, diethylene glycol, triethylene glycol, and of formula:
HOOC--Rg c--l--O--R6~O--Icl--Rg c--lt--OH
o o o in which t is 2 1, R6 represents the moiety of a diol, and Rg is the moiety of a diacid and/or an acid anhydride, ~ j 7 51 5 ~
c) a di-COOH terminated polyether of formula HOC--Q--C--O--polyethe~--R Q IlOH
O O O O
in which Q is a (CH2)n type hydrocarbon chain, n being comprised between 1 and 24, one or several carbon atoms that may be mono- or di-substituted, the polyether being obtained by chemical modification of a di-OH
polyether such as the reaction with 2 moles of a di-acid, per mole of polyether, said di-OH polyether being able to be polyethylene glycol, polypropylene glycol, polytetramethylene glycol or copolymers thereof.
d) a tri-block (a = 1) or poly-block (a > 1) oligomer of formula:
H O C--polyamide--ICl--[--O--polyether--O--ICl--polyamide--ICl la--O H
O O O O
obtained from di-COOH terminal polyamide and di-OH terminal polyether, such as those described above, e) an oligomer obtained by substituting each polyamide block in an oligomer of the above formula by a polyester block, in other words a tri-block (a = 1) oligomer or poly-block (a > 1) oligomer of formula:
H O ICl--polyester--- ICl--- [--O--polyether----I I--- polyester--C ---] O H
O o O o The oligomers HO--C--P--C--OH
Il 11 O O
employed preferably have a viscosity in solution, determined in meta-cresol at 30C and concentrations of 0.5 g/dl, comprised between 0.05 and 0.50 dl 9-~, and number average molar mass Mn comprised between 300 and 5000.
The polymers of the present invention are obtained by bulk addition reaction of oligomers of formula:
2175~51 HO--C--P--C--OH
Il 11 O O
and of bisimidazolines.
The bisimidazolines are compounds of general formula:
N=C R C R' R--NH NH
in which R and R' are as defined above.
The invention also relates to a process for preparing the 1 0 bisimidazolines.
Four types of synthesis reactions leading to bisimidazolines are described in the literature:
1- Direct synthesis by reaction between dinitriles and diamines without a catalyst, in ethanol solution or in the presence of catalysts such as sulfur or metallic salts, 2- Synthesis by reaction between dicarbothioamides and diamines, 3- Synthesis by reaction between diimidoesters and diamines, 4- Synthesis by reaction between dithiocarboxylates and diamines.
These reactions are reactions between diamines and derivatives of di-20 acids. The first type of reaction is the one that is preferably employed as thestarting diacid derivative, a dinitrile, is a much less expensive compound than the dithioamides, dithioesters and diimidoesters employed in the other types of synthesis.
Japanese patent JP 24 965 thus employs a reaction between dinitrile and diamine in the presence of sulfur. According to said Japanese patent, the bisimidazoline A can be obtained from adiponitrile and ethylene diamine.
NC--(CH2)4--CN + H2N--(cH2)2--NH2 1)S, 100C, 3 h , 2) Zn, 100 C, 1 h H I /C (CH2)4 ~ ~ H2 A
21 7~151 This process requires zinc to be added at the end of the reaction.
Under these conditions, it becomes somewhat difficult to purify the final bisimidazoline, and yields are low.
The process according to our invention consists in adding an aliphatic alcohol, having a boiling point above 80C, as the n-pentanol, during the first step, and eliminating the addition of zinc. Under these conditions, the starting materials remain in solution and the final product can be recovered by filtration before possibly being recrystallized. There is a distinct improvementin yields.
The addition or coupling reaction of oligomers of formula:
HO--C--P--C--OH
Il 11 O O
and bisimidazolines proceeds according to the following general schema:
N
/N=C R C/' `R' nHOOC--P~OOH + nR--NH NH
[NH--C--P--C--NH--R'--NH--C--R--C---NH--R'--]n O O O O
In order to carry out this synthesis, a temperature should be chosen such that the viscosity of the oligomer is sufficiently low, and notably below 500 Pa.s, and preferably less than 300 Pa.s so that the chain coupler molecules can become dispersed and incorporate and/or solublize themselves in the oligomer. This temperature is comprised between 100 and 350C, and is preferably between 150 and 330C.
The duration of the reaction under inert atmosphere is comprised between 1 and 120 minutes, preferably between 5 and 30 minutes, at atmospheric pressure.
It is also possible to obtain polymers according to the invention having solution viscosities determined in meta-cresol at 30C at concentrations of 0.5 g/dl that are higher than those of the starting oligomer (or oligomers) and which may attain, for example, values higher than 0.8 dl 9-~, having number average molecular masses Mn of high value, higher than 10,000, without eliminating by-products and without encountering the other difficulties inherent in conventional polycondensation reactions.
One or several chain couplers and one or several oligomers can be employed. Thus, concurrently or, on the contrary, successively, adding different oligomers makes it possible to obtain polymers with a greater or lesser degreee of randomization or blocking.
It is not necessary to use a catalyst, but this accelerates the reaction.
If used, 0.001 to 2% by weight, based on the oligomers and chain couplers, and preferably 0.01 to 0.5% of one or several conventional catalysts are 10 added, such as la 4,4'dimethylaminopyridine, paratoluenesulfonic acid, H3PO4, NaOH, or those disclosed in the applicant's European patent application EP-A -425,341.
Under these conditions, the reaction can be carried out in batch mode in an agitated reactor or in an extruder. A dry blend operation can then be used, or the coupler can be incorporate~ into the molten oligomer at a hopper of the extruder, introducing it continuously as a function of extruder throughput in order to maintain the stoechiometry of the reactive functions.
Preferably, the ratio ~N, [-COOH] / I- C ~ N H ,R ]
is maintained between 0.95 and 1.05 Because of this, the reaction product will include -COOH terminal groups if this ratio is above 1, the terminal groups below C~N\
NH,R' if this ratio is below 1, or these two terminal groups simultaneously if the ratio is equal to 1.
EXAM PLES
The following examples illustrate the invention.
In the examples:
- melting temperatures Tf and glass transition temperatures Tg were determined by Differential Scanning Calorimetry (DSC) (Du Pont 9900). The melting temperatures were determined at the maximum of the melting endotherm at a rate of heating of 20C/min, at the second passage following a heating cycle at 20C/min up to a temperature above the melting temperature of the sample analysed, followed by cooling at 40C/min down to ambient temperature.
- Mass loss was measured by thermogravimetry (TGA Du Pont 951) at 20C/min. T50,o corresponds to the temperature at which the product has lost 5% of its initial mass.
- Chemical derminations were conducted on a Mettler DL40 RC
apparatus. A blank assay was always carried out before the actual analysis 10 itself.
Acidity was titrated using an alcoholic solution of 0.1 N or 0.05N
potassium hydroxide, the sample being dissolved in a 1/1 (by vol) toluene/chloroform mixture or in benzyl alcohol at 40C when it was not soluble under the above conditions (this applied to oligomers, polymers and copolymers that contained polyamide units).
- The viscosity in solution llinh was determined in meta-cresol at 30C
at concentrations of 0.5 g/dl.
The chain couplers employed, and the starting oligomers were as follows:
Chain cou~lers:
H C--N~ ~N CH
H2C h ` cH2 A
CH3 ~CH3 \HC N ~ ~N CH
~C (CH2)4 C~ CH2 B
H C--N~ /N CH
H2C / \ ,CH2 N ~3 NH
E; F (See table 1).
Oligomers:
The oligomers I and 11 are depicted below:
HO C--(CH2) " - NH--C--(CH2),--C--NH - (C H2), ~--C--OH
_ --XO -- -- Y
X , y 2 0 X+y = 4.55 HO C--(C~2)11-NH--C--~CH2)~--C- NH-(CH2)"--C--O--(C~2)~--O
_ O --XO -- -- Y -- -- Z
O C--(cH2)n-NH--C--(CH2~,--C--NH-(CHZ)l,--C--OH
O O O _ O_ y, X X' y, y' 2 0 I I
X~y - X +y - 3,86 Z = 1 4, 1 9 Oligomer lll, having di-COOH terminal functions, is obtained from:
- terephtalic acid (T) - isophtalic acid (I) - lactame 1 2 (L1 2) - and from bis (4-amino-3-methyl cyclohexyl) methane (BMACM) with T/l/L 1 2/BMACM = 2. 8/1 . 2/3/3 (in moles) .
Oligomer IV is obtained from the same monomers with 10 Tll/L12/BMACM = 3.612.4/5/5 (in moles).
Oligomer V, having di-COOH terminal functions, is obtained from:
- terephtalic acid (T) - hexamethylene diamine (HMDA), - and lactame 1 Z (L1 2), with T/HMDA/L 1 2 - 6/5/6 (in moles) .
Unlike the oligomers lll and IV which are amorphous, the oligoamide V
is semi-crystalline.
The table below summarizes the characteristics of the starting oligomers:
Oligomers COOH ~ini~ Tf T5%
ter~.lin~l ~dlg~ ) i~n ~o C~ ( C~
functions (mol kg~1) 1 1.915 0.16 1045 145 355 Il 0.71 0.28 2817 151 340 lll 1.072 0.18 1865 -- 335 IV 0.667 0.25 3000 -- 348 V 0.775 0.18 2580 265 345 2 1 7 5 i ~ 1 Bisimidazoline 1~ R' A -(CH2)4- -CH2-CH2 -ICH2)4- -CH-CH2 ~H3 C -(CH2)5- -CH2-CH2 -IC~I2)~- -CH2-CH2 E -~CH2) 4- --C--CH2--D - ~()>-- _ -CH2-CH2 Table l E~fample 1: SY~heS~ of bisimidazoline A
In a 100 ml reactor provided with an anchor stirrer, witl1 an inlet for nitrogen and with a reflux cooler, and with oil batl1 heating, 19.83 g of 1,2 diaminoethane (0.33 mol), 17.84 g of 1,4-dicyanobutane (0.165 mol) and 0.59 of sulfur ~0.0156 mol) are stirred, under nitrogen blanket, until the sulfur dissolves (30 min). Following this, 50 ml of n-pentanol are added and the reaction mixture heated to 100C. Ammonia release is observed, thls terminating 3 hours after the beginning of the reaction. The reactor is then purged by sweeping with nitrogen for 1 hour, and then cooled down to room temperature. The bisimidazoline A is recovered by filtration, washed with n-pentanol and recrystallized in benzonitrile. Yield: 75.5 %. Mp = 221.6 C.
1H N.M.R. (250 MHz. CD30D. ref TMS): 1.79 (4H). 2.34 (4H). 3.51 ~8H) 4.98 (2H).
C10H18N4: Calc. (%) : C 61.82; H 9.34; N 28. 84 ~ound (%) : C 61.67; H 9.52; N 28.67 2 ~ 7 5 ~ 5 1 Comparative exam/Jle 1:
In the apparatus described in example 1, 19.83 9 of 1,2-diaminoethane (0.33 mol), 17.84 g of 1,4-dicyanobutane (0.165 mol) and 0.5 g of sulfur (0.0156 mol) are stirred, under nitrogen blanket, until the sulfur dissolves (30 min) after which the reaction mixture is heated at 100C for 3 hours. Following this, 5 9 of powdered zinc (0.076 mol) is added and heating is continued for a further hour. After cooling, the solidified reaction mixture is ground and suspended in 200 ml ethanol, heated for 2 h under reflux, and 10 filtered when hot. The filtrate is evaporated and the residue is recrystallized in benzonitrile. Yield of A: 36%
Example 2: S~vr~h~srs of bisimidazoline B:
The apparatus described in example 1 is employed with 24.46 9 of 1,2-diaminopropane (0.33 mol), 17.84 9 of 1,4-dicyanobutane (0.165 mol) and 0.5 y of sulfur (0.0156 mol). The reaction mixture is stirred under nitrogen atmosphere until the sulfur dissolves (30 min). After this, 50 ml of n-pentanol are added and the reaction mixture is heated to 100C. Release of ammonia is observed, this stopping 3 h after the beginning of the reaction.
20 The reactor is then purged by sweeping it with nitrogen for 1 h, after which it is cooled down to room temperature. The bisimidazoline B is recovered after evaporation of the n-pentanol by recrystallization in the tetrahydrofurane.
Yield: 61.2 %.Tf = 123.4 C.
1 H N.M.R. (250 MHz. CDCI3, TMS): 1.02 (6H). 1.51 (4H). 2.07 (4H).
2.95 (2H). 3.51 (2H). 3.75 (2H). 5.00 (2H).
C~2H22N4: Calc. (%) : C 64.83; H 9.97; N 25.20 Found (%) : C 64.21; H 10.10; N 24.96 Comparative exam~le 2:
In the apparatus described in example 1, 24.46 9 of 1,2-diaminopropane (0.33 mol), 17.84 9 of 1,4-dicyanobutane (0.165 mol) and 0.5 g of sulfur ~0.0156 mol) are stirred under nitrogen atmosphere until the sulfur dissolves (30 min) after which the reaction mixture is heated at 100C
for 3 h. Following this, 5 9 of zinc powder (0.076 mol) are added and heating is continued a further 1 h. After cooling, the solidified reaction mixture is ground and suspended in 200 ml of tetrahydrofurane (THF), heated for 2 h under reflux, and filtered hot. The bisimidazoline B precipitates when cold and is recovered by filtration and then recrystallized in the THF. Yield ofB: 40%.
21 7~1 51 Example 3: Synthesis of bisimidazoline C
The apparatus and procedure described in example 1 are employed with 19.43 g of 1,2-diaminoethane (0.33 mol), 22.47 g of 1,6-dicyanohexane (0.165 mol) and 0.5 g of sulfur (0.0156 mol). Yield: 66.7 %. Tf = 199.2 C.
1H N.M.R. (250 MHz. CD30D. ref TMS): 1.57 (2H). 1.78 (4H). 2.39 (4H). 3.71 (8H). 5.16 (2H).
C12H22N4 :Calc. (/0) : C 64.83; H 9.97; N 25.20 Found (%) : C 64.75; H 9.76; N 25.00 Example 4: Syr,lhesis of bisimidazoline D
In the apparatus described in example 1, 19.83 g of 1,2-diaminoethane (0.33 mol), 21.31 g of 1,4-dicyanobenzene (0.165 mol) and 0.5 g of sulfur (0.0156 mol) are stirred under nitrogen atmosphere until the sulfur dissolves (30 min~ after which the reaction mixture is heated at 100C
Release of ammonia is observed, which stops 3 hours after the start of the reaction. The reactor is then purged by sweeping it with nitrogen for 1 h, after which it is cooled down to room temperature. The bisimidazoline D is recovered by filtration, suspended in benzonitrile at 180 C, filtered, washed 20 with acetone and vacuum dried: 55.2 %.
Mp = 308.3 C.
1 H N.M.R. (250 MHz. 1.1.1.3.3.3-hexafluoro-2-propanol-d/CDCI3 (1/1 vol),. TMS): 4.12 (8H). 7.94 (4H).
C,2H14N4: Calc. (%) : C 67.27; H 6.59; N 26.15 Found (%) : C 67.31; H 6.55; N 25.80 Example 5: S~/n~hesis of L.i3i",iJazoline E
The apparatus and procedure employed in Example 1 are used with:
29.09 g of 2.2-dimethyl-1.2-diaminoethane (0.33 mol). 17.84 g of 1.4-dicyanobutane (0.165 mol) and 0.5 g of sulfur (0.0156 mol).
Yield: 53.9 %. Mp = 150.9 C.
N.M.R. 1H (250 MHz. CDCI3. ref TMS): 1.15 (12H). 1.58 (4H). 2.14 (4H). 3.21 (4H). 4.65 (2H).
C14H26N4: Calc. (%) : C 67.16; H 10.47; N 22.38 Found (%) : C 64.14; H 10.43; N 22.12 2i75l5~
Example 6: S~y"ll.esis of bisimidazoline F
The apparatus and procedure employed in Example 1 are used with:19.83 9 of 1.2-diaminoethane (0.33 moi). 20.16 9 of 1.5-dicyanopentane (0.165 mol) and 0.5 9 of sulfur (0.0156 mol). Yield: 57.4 %. Mp = 166.3 C.
1H N.M.R. (250 MHz. CD30D. ref TMS): 1.53 (4H). 1.76 (4H). 2.40 (4H~. 3.71 (8H). 5.18 (2H).
C11H20N4: Calc- : C 63.43; H 9.68; N 26.90 Found : C 63.33; H 9.82; N 26.74 ExamPle 7: Re--t;on of the oligoamide I wifh the bisimidazoline A
10.00 9 (9.57 mmol) of oligoamide I and 1.859 9 (9.57 mmol) of bisimidazoline A are fed into a 50 cm3 reactor fitted with oil bath heating, a nitrogen inlet and outlet and a mechanical anchor stirrer. The mixture is heated to 240 C with continued stirring for 30 minutes to yield, after cooling, a polymer having the following characteristics:
[COOH] = 0.12 mol/kg [ll]jnh = 54 dl/g Mp = 155 C
T5% = 414 C.
ExamPle 8: Reaction of the oligoamide I with the bisimidazoline B
10.00 9 (9.57 mmol) of oligoamide I and 2.128 9 9 (9.57 mmol) of bisimidazoline B are fed into a 50 cm3 reactor fitted with oil bath heating, a nitrogen inlet and outlet and a mechanical anchor agitator. The mixture is heated to 240 C with continuous stirring for 30 minutes to yield, after cooling, a polymer having the following characteristics:
[COOH] = 0.15 mol/kg [rl]inh = 0-45 dl/g Mp = 154 C
T5% = 408 C.
Example 9: Reaction of the oligoamide I with the bisimidazoline C
10.00 9 (9.57 mmol) of oligoamide I and 2.128 9 9 (9.57 mmol) of bisimidazoline C are fed into a 50 cm3 reactor fitted with oil bath heating, a nitrogen inlet and outlet and a mechanical anchor stirrer. The mixture is heated to 240 C with continued stirring for 30 minutes to yield, after cooling, a polymer having the following characteristics:
2 I 7 5 i 5 ~
[COOH] = 0.17 mol/kg [ll]jnh = 0.36 dl/g Mp = 153 C
T5% = 405 C.
Example 10: Reaction of oligoamide I with the bisimidazoline A
In a 100 cm3 mixer of the Brabender type fitted with a double contra-rotation blade stirrer and equipped with electrical heating and a nitrogen inletand output, 50.00 9 (47.87 mmol) of oligoamide I and 9.30 9 (47.87 mmol) 10 of bisimidazoline A are introduced. The mixture is heated to 240C with stirring for 15 min to yield, after cooling, a polymer having the following characteristics:
[COOH] = 0.07 mol/kg [ll];nh = 0.85 dl/g Mp = 156 C
T5% = 412 C.
Example 71: Reaction of tri-block oligomer ll with bisin.iJazoline A
In a reactor of 50 cm3 fitted with oil bath heating, a nitrogen inlet and outlet and a mechanical anchor stirrer, 10.00 9 (3.55 mmol) of tri-block oligomer ll and 0.690 9 (3.55 mmol) of bisimidazoline A are introduced. The mixture is heated to 240C under stirring for 30 min to yield, after cooling, a polymer having the following characteristics:
[COO H] = 0.16 mol/kg [ll]inh = 0.46 dl/g Mp = 152 C
Tso/0 = 401 C.
Example 12: Reaction of oliqoamide lll with bisimidazoline A
In a reactor of 250 cm~ provided with stirring and fitted with a system making it possible to work under inert (N2) atmosphere, 186.5 9 (0.1 moll f oligoamide lll and 19.43 9 (0.1 mol) of bisimidazoline A are introduced.
The reactor is plunged into an oil bath heated to 280C. The reaction mixture is stirred by an stirrer rotating at 50 rpm as soon as the viscosity of the medium has fallen to a sufficient level to allow this. After 15 minutes at 280C, a rapid increase in viscosity of the reaction mixture is observed, requiring the stirring speed to be reduced to 10 rpm. After 10 minutes under these conditions, the reaction is stopped.
The polymer obtained is translucent and only exhibits, according to thermal analysis, glass transition at 171 C.
Its viscosity in solution is 0.95 dl 9-1.
Example 13: Reaction of oligoamide IV with bfsimidazoline A
In the same reactor as the one described in example 12, 150 g 0.05 mol) of oligoamide IV and 9.71 9 (0.05 mol) of bisimidazoline A are introduced. Working under conditions similar to those of example 12, a change in reaction mixture viscosity is observed after 10 minutes at 280C
requiring the speed of stirring to be reduced. The reaction is stopped within the five minutes that follow.
The polymer obtained is translucent and only exhibits, according to thermal analysis glass transition at 174C. Its viscosity in solution is 0.85 dl g 1 Example 14: Reaction of'oligoamide V with bisimidazoline D
In the reactor described in example 11, 25.80 g (0.01 mol) of oligoamide V and 2.14 g (0.01 mol) of bisimidazoline D are introduced. The reactor is plunged into a bath set at 295C. The reaction mixture becomes fluid after 5 minutes at this temperature. It is then stirred at a speed of 50 rpm for 15 minutes. Following this, the speed of stirring is reduced to 10 rpm and the reaction is continued for a further 5 minutes before being stopped.
The polymer obtained has a whitish opaque appearance. Its viscosity is 0.70 dl g-1.
Thermal analysis shows, apart from glass transition at 80C, a melting point of 278C.
Rl represents the moiety of the organic di-acid employed as a chain terminator;
x and y are integers 2 0 such that x + y 2 1.
Such a polyamide can be obtained from:
- a lactame of formula co and/or aminoacid of formula H2N--R2--COOH and diamine H2N--R4--NH2, in the presence of an excess of di-acid of formula HOOC--R3--COOH .
The lactames of formula:
2l l5~51 NH
R/ I
2~co are for exmple C5 - C14 lactames such as caprolactames, dodecalactames .
The aminoacids of formula H2N--R2~OOH are for example aliphatic C5 - C24 aminoacids such as 11-amino-undecanoic acid.
The diacids of formula HOOC--Rl--COOH and HOOC--R3--COOH:
- aromatic di-acids, for example iso and terephtalic acids, dicarboxylic (in position 2,6; 1,5 ;2,7) naphtalene acids, 4,4'-dicarboxydiphenylether, 4,4'-dicarboxybiphenyl acids, - aliphatic diacids or anhydrides, for example which are for example branched or straight-chain C4 to C24 acids such as adipic, sebacic, decane-1,10-dioic, 1-dodecane, 12- dioic, fumaric acids, maleic anhydride, - cycloaliphatic di-acids such as cyclohexane-1,4-dicarboxylic acid.
The diamines of formula H2N--R4--NH2 can be:
- cycloaliphatic diamines, for example optionally methane-substituted 4,4'-diamino-dicyclohexyl such as bis (4-amino-3-methylcyclohexyl) methane, isophorone diamine, - aliphatic diamines, for example branched or straight chain C4 to C24 diamines, such as 1 ,6-hexamethylene-diamine, 1 ,1 2-dodecamethylene-20 diamine.
Examples of such oligomers are disclosed in EP-A-0,281,461 and EP-A-0,31 3,436.
b) a polyester with di-COOH terminations having an aliphatic or semi-aromatic structure that may be mono- or poly-olefinically unsaturated, obtained from excess di-acid and/or acid anhydride, such as succinic or phtalic anhydride, and those cited above, and diol, such as C2 to C24 linear or branched aliphatic diol, for example ethylene glycol, propylene glycol, 1,4-butane-dio-l, 1-5-pentane-diol, 1,6-hexane-diol, diethylene glycol, triethylene glycol, and of formula:
HOOC--Rg c--l--O--R6~O--Icl--Rg c--lt--OH
o o o in which t is 2 1, R6 represents the moiety of a diol, and Rg is the moiety of a diacid and/or an acid anhydride, ~ j 7 51 5 ~
c) a di-COOH terminated polyether of formula HOC--Q--C--O--polyethe~--R Q IlOH
O O O O
in which Q is a (CH2)n type hydrocarbon chain, n being comprised between 1 and 24, one or several carbon atoms that may be mono- or di-substituted, the polyether being obtained by chemical modification of a di-OH
polyether such as the reaction with 2 moles of a di-acid, per mole of polyether, said di-OH polyether being able to be polyethylene glycol, polypropylene glycol, polytetramethylene glycol or copolymers thereof.
d) a tri-block (a = 1) or poly-block (a > 1) oligomer of formula:
H O C--polyamide--ICl--[--O--polyether--O--ICl--polyamide--ICl la--O H
O O O O
obtained from di-COOH terminal polyamide and di-OH terminal polyether, such as those described above, e) an oligomer obtained by substituting each polyamide block in an oligomer of the above formula by a polyester block, in other words a tri-block (a = 1) oligomer or poly-block (a > 1) oligomer of formula:
H O ICl--polyester--- ICl--- [--O--polyether----I I--- polyester--C ---] O H
O o O o The oligomers HO--C--P--C--OH
Il 11 O O
employed preferably have a viscosity in solution, determined in meta-cresol at 30C and concentrations of 0.5 g/dl, comprised between 0.05 and 0.50 dl 9-~, and number average molar mass Mn comprised between 300 and 5000.
The polymers of the present invention are obtained by bulk addition reaction of oligomers of formula:
2175~51 HO--C--P--C--OH
Il 11 O O
and of bisimidazolines.
The bisimidazolines are compounds of general formula:
N=C R C R' R--NH NH
in which R and R' are as defined above.
The invention also relates to a process for preparing the 1 0 bisimidazolines.
Four types of synthesis reactions leading to bisimidazolines are described in the literature:
1- Direct synthesis by reaction between dinitriles and diamines without a catalyst, in ethanol solution or in the presence of catalysts such as sulfur or metallic salts, 2- Synthesis by reaction between dicarbothioamides and diamines, 3- Synthesis by reaction between diimidoesters and diamines, 4- Synthesis by reaction between dithiocarboxylates and diamines.
These reactions are reactions between diamines and derivatives of di-20 acids. The first type of reaction is the one that is preferably employed as thestarting diacid derivative, a dinitrile, is a much less expensive compound than the dithioamides, dithioesters and diimidoesters employed in the other types of synthesis.
Japanese patent JP 24 965 thus employs a reaction between dinitrile and diamine in the presence of sulfur. According to said Japanese patent, the bisimidazoline A can be obtained from adiponitrile and ethylene diamine.
NC--(CH2)4--CN + H2N--(cH2)2--NH2 1)S, 100C, 3 h , 2) Zn, 100 C, 1 h H I /C (CH2)4 ~ ~ H2 A
21 7~151 This process requires zinc to be added at the end of the reaction.
Under these conditions, it becomes somewhat difficult to purify the final bisimidazoline, and yields are low.
The process according to our invention consists in adding an aliphatic alcohol, having a boiling point above 80C, as the n-pentanol, during the first step, and eliminating the addition of zinc. Under these conditions, the starting materials remain in solution and the final product can be recovered by filtration before possibly being recrystallized. There is a distinct improvementin yields.
The addition or coupling reaction of oligomers of formula:
HO--C--P--C--OH
Il 11 O O
and bisimidazolines proceeds according to the following general schema:
N
/N=C R C/' `R' nHOOC--P~OOH + nR--NH NH
[NH--C--P--C--NH--R'--NH--C--R--C---NH--R'--]n O O O O
In order to carry out this synthesis, a temperature should be chosen such that the viscosity of the oligomer is sufficiently low, and notably below 500 Pa.s, and preferably less than 300 Pa.s so that the chain coupler molecules can become dispersed and incorporate and/or solublize themselves in the oligomer. This temperature is comprised between 100 and 350C, and is preferably between 150 and 330C.
The duration of the reaction under inert atmosphere is comprised between 1 and 120 minutes, preferably between 5 and 30 minutes, at atmospheric pressure.
It is also possible to obtain polymers according to the invention having solution viscosities determined in meta-cresol at 30C at concentrations of 0.5 g/dl that are higher than those of the starting oligomer (or oligomers) and which may attain, for example, values higher than 0.8 dl 9-~, having number average molecular masses Mn of high value, higher than 10,000, without eliminating by-products and without encountering the other difficulties inherent in conventional polycondensation reactions.
One or several chain couplers and one or several oligomers can be employed. Thus, concurrently or, on the contrary, successively, adding different oligomers makes it possible to obtain polymers with a greater or lesser degreee of randomization or blocking.
It is not necessary to use a catalyst, but this accelerates the reaction.
If used, 0.001 to 2% by weight, based on the oligomers and chain couplers, and preferably 0.01 to 0.5% of one or several conventional catalysts are 10 added, such as la 4,4'dimethylaminopyridine, paratoluenesulfonic acid, H3PO4, NaOH, or those disclosed in the applicant's European patent application EP-A -425,341.
Under these conditions, the reaction can be carried out in batch mode in an agitated reactor or in an extruder. A dry blend operation can then be used, or the coupler can be incorporate~ into the molten oligomer at a hopper of the extruder, introducing it continuously as a function of extruder throughput in order to maintain the stoechiometry of the reactive functions.
Preferably, the ratio ~N, [-COOH] / I- C ~ N H ,R ]
is maintained between 0.95 and 1.05 Because of this, the reaction product will include -COOH terminal groups if this ratio is above 1, the terminal groups below C~N\
NH,R' if this ratio is below 1, or these two terminal groups simultaneously if the ratio is equal to 1.
EXAM PLES
The following examples illustrate the invention.
In the examples:
- melting temperatures Tf and glass transition temperatures Tg were determined by Differential Scanning Calorimetry (DSC) (Du Pont 9900). The melting temperatures were determined at the maximum of the melting endotherm at a rate of heating of 20C/min, at the second passage following a heating cycle at 20C/min up to a temperature above the melting temperature of the sample analysed, followed by cooling at 40C/min down to ambient temperature.
- Mass loss was measured by thermogravimetry (TGA Du Pont 951) at 20C/min. T50,o corresponds to the temperature at which the product has lost 5% of its initial mass.
- Chemical derminations were conducted on a Mettler DL40 RC
apparatus. A blank assay was always carried out before the actual analysis 10 itself.
Acidity was titrated using an alcoholic solution of 0.1 N or 0.05N
potassium hydroxide, the sample being dissolved in a 1/1 (by vol) toluene/chloroform mixture or in benzyl alcohol at 40C when it was not soluble under the above conditions (this applied to oligomers, polymers and copolymers that contained polyamide units).
- The viscosity in solution llinh was determined in meta-cresol at 30C
at concentrations of 0.5 g/dl.
The chain couplers employed, and the starting oligomers were as follows:
Chain cou~lers:
H C--N~ ~N CH
H2C h ` cH2 A
CH3 ~CH3 \HC N ~ ~N CH
~C (CH2)4 C~ CH2 B
H C--N~ /N CH
H2C / \ ,CH2 N ~3 NH
E; F (See table 1).
Oligomers:
The oligomers I and 11 are depicted below:
HO C--(CH2) " - NH--C--(CH2),--C--NH - (C H2), ~--C--OH
_ --XO -- -- Y
X , y 2 0 X+y = 4.55 HO C--(C~2)11-NH--C--~CH2)~--C- NH-(CH2)"--C--O--(C~2)~--O
_ O --XO -- -- Y -- -- Z
O C--(cH2)n-NH--C--(CH2~,--C--NH-(CHZ)l,--C--OH
O O O _ O_ y, X X' y, y' 2 0 I I
X~y - X +y - 3,86 Z = 1 4, 1 9 Oligomer lll, having di-COOH terminal functions, is obtained from:
- terephtalic acid (T) - isophtalic acid (I) - lactame 1 2 (L1 2) - and from bis (4-amino-3-methyl cyclohexyl) methane (BMACM) with T/l/L 1 2/BMACM = 2. 8/1 . 2/3/3 (in moles) .
Oligomer IV is obtained from the same monomers with 10 Tll/L12/BMACM = 3.612.4/5/5 (in moles).
Oligomer V, having di-COOH terminal functions, is obtained from:
- terephtalic acid (T) - hexamethylene diamine (HMDA), - and lactame 1 Z (L1 2), with T/HMDA/L 1 2 - 6/5/6 (in moles) .
Unlike the oligomers lll and IV which are amorphous, the oligoamide V
is semi-crystalline.
The table below summarizes the characteristics of the starting oligomers:
Oligomers COOH ~ini~ Tf T5%
ter~.lin~l ~dlg~ ) i~n ~o C~ ( C~
functions (mol kg~1) 1 1.915 0.16 1045 145 355 Il 0.71 0.28 2817 151 340 lll 1.072 0.18 1865 -- 335 IV 0.667 0.25 3000 -- 348 V 0.775 0.18 2580 265 345 2 1 7 5 i ~ 1 Bisimidazoline 1~ R' A -(CH2)4- -CH2-CH2 -ICH2)4- -CH-CH2 ~H3 C -(CH2)5- -CH2-CH2 -IC~I2)~- -CH2-CH2 E -~CH2) 4- --C--CH2--D - ~()>-- _ -CH2-CH2 Table l E~fample 1: SY~heS~ of bisimidazoline A
In a 100 ml reactor provided with an anchor stirrer, witl1 an inlet for nitrogen and with a reflux cooler, and with oil batl1 heating, 19.83 g of 1,2 diaminoethane (0.33 mol), 17.84 g of 1,4-dicyanobutane (0.165 mol) and 0.59 of sulfur ~0.0156 mol) are stirred, under nitrogen blanket, until the sulfur dissolves (30 min). Following this, 50 ml of n-pentanol are added and the reaction mixture heated to 100C. Ammonia release is observed, thls terminating 3 hours after the beginning of the reaction. The reactor is then purged by sweeping with nitrogen for 1 hour, and then cooled down to room temperature. The bisimidazoline A is recovered by filtration, washed with n-pentanol and recrystallized in benzonitrile. Yield: 75.5 %. Mp = 221.6 C.
1H N.M.R. (250 MHz. CD30D. ref TMS): 1.79 (4H). 2.34 (4H). 3.51 ~8H) 4.98 (2H).
C10H18N4: Calc. (%) : C 61.82; H 9.34; N 28. 84 ~ound (%) : C 61.67; H 9.52; N 28.67 2 ~ 7 5 ~ 5 1 Comparative exam/Jle 1:
In the apparatus described in example 1, 19.83 9 of 1,2-diaminoethane (0.33 mol), 17.84 g of 1,4-dicyanobutane (0.165 mol) and 0.5 g of sulfur (0.0156 mol) are stirred, under nitrogen blanket, until the sulfur dissolves (30 min) after which the reaction mixture is heated at 100C for 3 hours. Following this, 5 9 of powdered zinc (0.076 mol) is added and heating is continued for a further hour. After cooling, the solidified reaction mixture is ground and suspended in 200 ml ethanol, heated for 2 h under reflux, and 10 filtered when hot. The filtrate is evaporated and the residue is recrystallized in benzonitrile. Yield of A: 36%
Example 2: S~vr~h~srs of bisimidazoline B:
The apparatus described in example 1 is employed with 24.46 9 of 1,2-diaminopropane (0.33 mol), 17.84 9 of 1,4-dicyanobutane (0.165 mol) and 0.5 y of sulfur (0.0156 mol). The reaction mixture is stirred under nitrogen atmosphere until the sulfur dissolves (30 min). After this, 50 ml of n-pentanol are added and the reaction mixture is heated to 100C. Release of ammonia is observed, this stopping 3 h after the beginning of the reaction.
20 The reactor is then purged by sweeping it with nitrogen for 1 h, after which it is cooled down to room temperature. The bisimidazoline B is recovered after evaporation of the n-pentanol by recrystallization in the tetrahydrofurane.
Yield: 61.2 %.Tf = 123.4 C.
1 H N.M.R. (250 MHz. CDCI3, TMS): 1.02 (6H). 1.51 (4H). 2.07 (4H).
2.95 (2H). 3.51 (2H). 3.75 (2H). 5.00 (2H).
C~2H22N4: Calc. (%) : C 64.83; H 9.97; N 25.20 Found (%) : C 64.21; H 10.10; N 24.96 Comparative exam~le 2:
In the apparatus described in example 1, 24.46 9 of 1,2-diaminopropane (0.33 mol), 17.84 9 of 1,4-dicyanobutane (0.165 mol) and 0.5 g of sulfur ~0.0156 mol) are stirred under nitrogen atmosphere until the sulfur dissolves (30 min) after which the reaction mixture is heated at 100C
for 3 h. Following this, 5 9 of zinc powder (0.076 mol) are added and heating is continued a further 1 h. After cooling, the solidified reaction mixture is ground and suspended in 200 ml of tetrahydrofurane (THF), heated for 2 h under reflux, and filtered hot. The bisimidazoline B precipitates when cold and is recovered by filtration and then recrystallized in the THF. Yield ofB: 40%.
21 7~1 51 Example 3: Synthesis of bisimidazoline C
The apparatus and procedure described in example 1 are employed with 19.43 g of 1,2-diaminoethane (0.33 mol), 22.47 g of 1,6-dicyanohexane (0.165 mol) and 0.5 g of sulfur (0.0156 mol). Yield: 66.7 %. Tf = 199.2 C.
1H N.M.R. (250 MHz. CD30D. ref TMS): 1.57 (2H). 1.78 (4H). 2.39 (4H). 3.71 (8H). 5.16 (2H).
C12H22N4 :Calc. (/0) : C 64.83; H 9.97; N 25.20 Found (%) : C 64.75; H 9.76; N 25.00 Example 4: Syr,lhesis of bisimidazoline D
In the apparatus described in example 1, 19.83 g of 1,2-diaminoethane (0.33 mol), 21.31 g of 1,4-dicyanobenzene (0.165 mol) and 0.5 g of sulfur (0.0156 mol) are stirred under nitrogen atmosphere until the sulfur dissolves (30 min~ after which the reaction mixture is heated at 100C
Release of ammonia is observed, which stops 3 hours after the start of the reaction. The reactor is then purged by sweeping it with nitrogen for 1 h, after which it is cooled down to room temperature. The bisimidazoline D is recovered by filtration, suspended in benzonitrile at 180 C, filtered, washed 20 with acetone and vacuum dried: 55.2 %.
Mp = 308.3 C.
1 H N.M.R. (250 MHz. 1.1.1.3.3.3-hexafluoro-2-propanol-d/CDCI3 (1/1 vol),. TMS): 4.12 (8H). 7.94 (4H).
C,2H14N4: Calc. (%) : C 67.27; H 6.59; N 26.15 Found (%) : C 67.31; H 6.55; N 25.80 Example 5: S~/n~hesis of L.i3i",iJazoline E
The apparatus and procedure employed in Example 1 are used with:
29.09 g of 2.2-dimethyl-1.2-diaminoethane (0.33 mol). 17.84 g of 1.4-dicyanobutane (0.165 mol) and 0.5 g of sulfur (0.0156 mol).
Yield: 53.9 %. Mp = 150.9 C.
N.M.R. 1H (250 MHz. CDCI3. ref TMS): 1.15 (12H). 1.58 (4H). 2.14 (4H). 3.21 (4H). 4.65 (2H).
C14H26N4: Calc. (%) : C 67.16; H 10.47; N 22.38 Found (%) : C 64.14; H 10.43; N 22.12 2i75l5~
Example 6: S~y"ll.esis of bisimidazoline F
The apparatus and procedure employed in Example 1 are used with:19.83 9 of 1.2-diaminoethane (0.33 moi). 20.16 9 of 1.5-dicyanopentane (0.165 mol) and 0.5 9 of sulfur (0.0156 mol). Yield: 57.4 %. Mp = 166.3 C.
1H N.M.R. (250 MHz. CD30D. ref TMS): 1.53 (4H). 1.76 (4H). 2.40 (4H~. 3.71 (8H). 5.18 (2H).
C11H20N4: Calc- : C 63.43; H 9.68; N 26.90 Found : C 63.33; H 9.82; N 26.74 ExamPle 7: Re--t;on of the oligoamide I wifh the bisimidazoline A
10.00 9 (9.57 mmol) of oligoamide I and 1.859 9 (9.57 mmol) of bisimidazoline A are fed into a 50 cm3 reactor fitted with oil bath heating, a nitrogen inlet and outlet and a mechanical anchor stirrer. The mixture is heated to 240 C with continued stirring for 30 minutes to yield, after cooling, a polymer having the following characteristics:
[COOH] = 0.12 mol/kg [ll]jnh = 54 dl/g Mp = 155 C
T5% = 414 C.
ExamPle 8: Reaction of the oligoamide I with the bisimidazoline B
10.00 9 (9.57 mmol) of oligoamide I and 2.128 9 9 (9.57 mmol) of bisimidazoline B are fed into a 50 cm3 reactor fitted with oil bath heating, a nitrogen inlet and outlet and a mechanical anchor agitator. The mixture is heated to 240 C with continuous stirring for 30 minutes to yield, after cooling, a polymer having the following characteristics:
[COOH] = 0.15 mol/kg [rl]inh = 0-45 dl/g Mp = 154 C
T5% = 408 C.
Example 9: Reaction of the oligoamide I with the bisimidazoline C
10.00 9 (9.57 mmol) of oligoamide I and 2.128 9 9 (9.57 mmol) of bisimidazoline C are fed into a 50 cm3 reactor fitted with oil bath heating, a nitrogen inlet and outlet and a mechanical anchor stirrer. The mixture is heated to 240 C with continued stirring for 30 minutes to yield, after cooling, a polymer having the following characteristics:
2 I 7 5 i 5 ~
[COOH] = 0.17 mol/kg [ll]jnh = 0.36 dl/g Mp = 153 C
T5% = 405 C.
Example 10: Reaction of oligoamide I with the bisimidazoline A
In a 100 cm3 mixer of the Brabender type fitted with a double contra-rotation blade stirrer and equipped with electrical heating and a nitrogen inletand output, 50.00 9 (47.87 mmol) of oligoamide I and 9.30 9 (47.87 mmol) 10 of bisimidazoline A are introduced. The mixture is heated to 240C with stirring for 15 min to yield, after cooling, a polymer having the following characteristics:
[COOH] = 0.07 mol/kg [ll];nh = 0.85 dl/g Mp = 156 C
T5% = 412 C.
Example 71: Reaction of tri-block oligomer ll with bisin.iJazoline A
In a reactor of 50 cm3 fitted with oil bath heating, a nitrogen inlet and outlet and a mechanical anchor stirrer, 10.00 9 (3.55 mmol) of tri-block oligomer ll and 0.690 9 (3.55 mmol) of bisimidazoline A are introduced. The mixture is heated to 240C under stirring for 30 min to yield, after cooling, a polymer having the following characteristics:
[COO H] = 0.16 mol/kg [ll]inh = 0.46 dl/g Mp = 152 C
Tso/0 = 401 C.
Example 12: Reaction of oliqoamide lll with bisimidazoline A
In a reactor of 250 cm~ provided with stirring and fitted with a system making it possible to work under inert (N2) atmosphere, 186.5 9 (0.1 moll f oligoamide lll and 19.43 9 (0.1 mol) of bisimidazoline A are introduced.
The reactor is plunged into an oil bath heated to 280C. The reaction mixture is stirred by an stirrer rotating at 50 rpm as soon as the viscosity of the medium has fallen to a sufficient level to allow this. After 15 minutes at 280C, a rapid increase in viscosity of the reaction mixture is observed, requiring the stirring speed to be reduced to 10 rpm. After 10 minutes under these conditions, the reaction is stopped.
The polymer obtained is translucent and only exhibits, according to thermal analysis, glass transition at 171 C.
Its viscosity in solution is 0.95 dl 9-1.
Example 13: Reaction of oligoamide IV with bfsimidazoline A
In the same reactor as the one described in example 12, 150 g 0.05 mol) of oligoamide IV and 9.71 9 (0.05 mol) of bisimidazoline A are introduced. Working under conditions similar to those of example 12, a change in reaction mixture viscosity is observed after 10 minutes at 280C
requiring the speed of stirring to be reduced. The reaction is stopped within the five minutes that follow.
The polymer obtained is translucent and only exhibits, according to thermal analysis glass transition at 174C. Its viscosity in solution is 0.85 dl g 1 Example 14: Reaction of'oligoamide V with bisimidazoline D
In the reactor described in example 11, 25.80 g (0.01 mol) of oligoamide V and 2.14 g (0.01 mol) of bisimidazoline D are introduced. The reactor is plunged into a bath set at 295C. The reaction mixture becomes fluid after 5 minutes at this temperature. It is then stirred at a speed of 50 rpm for 15 minutes. Following this, the speed of stirring is reduced to 10 rpm and the reaction is continued for a further 5 minutes before being stopped.
The polymer obtained has a whitish opaque appearance. Its viscosity is 0.70 dl g-1.
Thermal analysis shows, apart from glass transition at 80C, a melting point of 278C.
Claims (11)
1. Polymers and copolymers comprising at least one recurring unit of formula:
in which:
R is a single bond, a linear hydrocarbon chain R' is an aliphatic or aromatic hydrocarbon chain, which may be substituted, and of which the shortest chain linking the two neighboring -NH- units comprises two or three carbon atoms, and is the moiety of an ologomer of formula:
in which:
R is a single bond, a linear hydrocarbon chain R' is an aliphatic or aromatic hydrocarbon chain, which may be substituted, and of which the shortest chain linking the two neighboring -NH- units comprises two or three carbon atoms, and is the moiety of an ologomer of formula:
2. Polymers and copolymers according to Claim 1, in which R is a ?(CH2)p? group with p = 4 or 6.
3. Polymers and copolymers according to Claim 1 in which R is a paraphenylene group.
4. Polymers and copolymers according to any one of Claims 1 to 3, wherein R' is a ?(CH2)2?, ?CH(CH3)?CH2? group.
5. Polymers and copolymers according to any one of Claims 1 to 4.
wherein:
is the moiety of an oligomer comprising:
- one or several polyamide blocks, and/or - one several polyester blocks, and/or - one or several polyether blocks.
wherein:
is the moiety of an oligomer comprising:
- one or several polyamide blocks, and/or - one several polyester blocks, and/or - one or several polyether blocks.
6. A process for obtaining polymers and copolymers comprising at least one recurring unit of formula:
wherein:
R is a single bond, a linear hydrocarbon chain R' is an aliphatic or aromatic hydrocarbon chain, which may be substituted, and of which the shortest chain linking the two neighboring -NH- units carries two or three carbon atoms, and is the moiety of an ologomer of formula:
by means of a bulk addition reaction of one or several of the following oligomer(s) with one or several bisimidazoline(s) of formula(e):
at a temperture higher than the melting point of the oligomer or oligomers, at atmospheric pressure.
wherein:
R is a single bond, a linear hydrocarbon chain R' is an aliphatic or aromatic hydrocarbon chain, which may be substituted, and of which the shortest chain linking the two neighboring -NH- units carries two or three carbon atoms, and is the moiety of an ologomer of formula:
by means of a bulk addition reaction of one or several of the following oligomer(s) with one or several bisimidazoline(s) of formula(e):
at a temperture higher than the melting point of the oligomer or oligomers, at atmospheric pressure.
7. The process according to claim 6, wherein a reaction mixture temperature of between 100 and 350°C is selected whereby the viscosity of the oligomer or oligomers is less than 500 Pa.s, and wherein the duration of the reaction is comprised between 1 and 120 minutes.
8 The process according to claim 6 or 7, wherein 0.001 to 2% by weight, based on the oligomers and bisimidazolines of one or more than one catalyst(s) is added to the reaction mixture.
9. The process according to any one of claims 6 to 8, wherein the bulk addition reaction is carried out in a batch process in a stirred reactor, or continuously in an extruder, or in a continuous reactor.
10. Process for preparing bisimidazolines from dinitriles and diamines characterized by the addition of an aliphatic alcohol having a boiling point greater than 80° C.
11. The process according to claim 10, wherein said aliphatic alcohol is n-pentanol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9505061 | 1995-04-27 | ||
| FR9505061A FR2733757B1 (en) | 1995-04-27 | 1995-04-27 | POLYMERS AND COPOLYMERS FROM THE ADDITION OF DI-CARBOXY TERMINAL OLIGOMERS AND BISIMIDAZOLINES, AND PROCESS FOR OBTAINING THEM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2175151A1 true CA2175151A1 (en) | 1996-10-28 |
Family
ID=9478504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002175151A Abandoned CA2175151A1 (en) | 1995-04-27 | 1996-04-26 | Di-carboxy terminated oligomer and bisimidazoline addition polymers and copolymers and process for obtaining them |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0739924A1 (en) |
| JP (1) | JPH08337649A (en) |
| KR (1) | KR960037721A (en) |
| CN (1) | CN1141930A (en) |
| CA (1) | CA2175151A1 (en) |
| FR (1) | FR2733757B1 (en) |
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| ES2670944T3 (en) * | 2011-07-21 | 2018-06-04 | Croda International Plc | Branched polyether polyamide block copolymers and methods of preparing and using them |
| FR2981653B1 (en) | 2011-10-25 | 2014-08-22 | Arkema France | THERMOPLASTIC COMPOSITE MATERIAL REINFORCED WITH SYNTHETIC FIBERS AND METHOD OF MANUFACTURE |
| FR2991331B1 (en) | 2012-06-01 | 2015-05-15 | Arkema France | THERMOPLASTIC COMPOSITE MATERIAL BASED ON NATURAL FIBERS |
| FR2997089B1 (en) | 2012-10-23 | 2015-11-13 | Arkema France | THERMOPLASTIC COMPOSITE MATERIAL BASED ON SEMI-CRYSTALLINE POLYAMIDE AND PROCESS FOR PRODUCING THE SAME |
| FR2997036B1 (en) | 2012-10-23 | 2015-01-16 | Arkema France | PROCESS FOR MANUFACTURING A CLOSED MOLDED THERMOPLASTIC COMPOSITE PIECE WITH INJECTION IN A COLD MOLD |
| FR2997035B1 (en) | 2012-10-23 | 2016-07-01 | Arkema France | METHOD FOR MANUFACTURING THERMOPLASTIC COMPOSITE PART, INJECTION-COMPRESSION-VACUUM MOLDING, DEVICE FOR IMPLEMENTATION AND PART THUS OBTAINED |
| FR3019824B1 (en) | 2014-04-15 | 2017-10-13 | Arkema France | PROCESS FOR COMPOSITE MATERIAL WITH THERMOPLASTIC POLYMER IMPREGNATION FROM PREPOLYMER AND CHAIN LENGTH |
| FR3019822B1 (en) | 2014-04-15 | 2017-10-20 | Arkema France | PROCESS FOR PRODUCING A THERMOPLASTIC MATERIAL BASED ON SEMI-CRYSTALLINE POLYAMIDE |
| FR3019827B1 (en) | 2014-04-15 | 2020-10-09 | Arkema France | COMPOSITION AND PROCESS FOR COMPOSITE MATERIAL WITH IMPREGNATION WITH SEMI-CRYSTALLINE POLYAMIDE, FROM A PREPOLYMER AND A CHAIN EXTENSION |
| FR3019826B1 (en) | 2014-04-15 | 2017-10-20 | Arkema France | THERMOPLASTIC COMPOSITION BASED ON POLYMER POLYAMIDE FROM PREPOLYMER AND CHAIN LENGTH AND METHOD OF MANUFACTURE |
| FR3026107B1 (en) | 2014-09-24 | 2018-02-16 | Arkema France | USE OF A BLOCK COPOLYMER FOR THE PROTECTION OF METAL-BASED PARTS |
| FR3032445A1 (en) | 2015-02-05 | 2016-08-12 | Arkema France | DELAYED COMBUSTIBILITY POLYAMIDE COMPOSITION |
| FR3049291B1 (en) | 2016-03-24 | 2018-03-23 | Compagnie Generale Des Etablissements Michelin | SELF-ADHERENT COMPOSITE ELEMENT COMPRISING A BLOCK COPOLYMER |
| FR3049282B1 (en) | 2016-03-24 | 2018-03-23 | Compagnie Generale Des Etablissements Michelin | REINFORCED PRODUCT COMPRISING A SELF-ADHESIVE COMPOSITE REINFORCEMENT COMPRISING A BLOCK COPOLYMER |
| FR3049281B1 (en) | 2016-03-24 | 2019-11-01 | Arkema France | BLOCK COPOLYMER FOR THE PROTECTION OF METAL-BASED PARTS |
| FR3049283B1 (en) | 2016-03-24 | 2018-03-23 | Compagnie Generale Des Etablissements Michelin | REINFORCED PRODUCT COMPRISING A SELF-ADHESIVE COMPOSITE REINFORCEMENT COMPRISING A BLOCK COPOLYMER |
| FR3053695B1 (en) | 2016-07-11 | 2018-07-06 | Arkema France | VITREOUS TRANSITION HIGH TEMPERATURE SEMI-CRYSTALLINE POLYAMIDE COMPOSITION FOR THERMOPLASTIC MATERIAL, METHOD FOR MANUFACTURING THE SAME AND USES THEREOF |
| FR3053696B1 (en) | 2016-07-11 | 2018-07-06 | Arkema France | VITREOUS TRANSITION HIGH TEMPERATURE SEMI-CRYSTALLINE POLYAMIDE COMPOSITION FOR COMPOSITE MATERIAL, MANUFACTURING METHOD AND USES THEREOF |
| FR3064272A1 (en) | 2017-03-24 | 2018-09-28 | Arkema France | SEMICALLY CRYSTALLINE POLYAMIDE COMPOSITION OF SHORT DIAMINE-BASED TRANSITION VITREOUS TEMPERATURE COMPOSITION FOR THERMOPLASTIC MATERIAL, METHOD FOR MANUFACTURING THE SAME AND USES THEREOF |
| FR3064271B1 (en) | 2017-03-24 | 2021-04-30 | Arkema France | COMPOSITION OF SEMI-CRYSTALLINE POLYAMIDE OF HIGH GLASS TRANSITION TEMPERATURE AND HIGH MELTING TEMPERATURE FOR THERMOPLASTIC MATERIAL, ITS MANUFACTURING PROCESS AND ITS USES |
| FR3067961B1 (en) | 2017-06-22 | 2020-11-06 | Arkema France | METHOD OF MANUFACTURING A FIBROUS MATERIAL IMPREGNATED WITH THERMOPLASTIC POLYMER |
| FR3067968B1 (en) | 2017-06-22 | 2020-11-06 | Arkema France | FIBROUS MATERIAL IMPREGNATED WITH THERMOPLASTIC POLYMER |
| FR3067969B1 (en) | 2017-06-22 | 2022-08-12 | Arkema France | FIBROUS MATERIAL IMPREGNATED WITH REACTIVE THERMOPLASTIC PREPOLYMER |
| FR3092786B1 (en) | 2019-02-19 | 2021-01-15 | Arkema France | PROCESS FOR MANUFACTURING A THERMOPLASTIC COMPOSITE PART IN A CLOSED MOLD, WITH INJECTION IN AN ISOTHERMAL MOLD |
| FR3098517B1 (en) | 2019-07-09 | 2021-06-04 | Arkema France | PROCESS FOR PREPARING A FIBROUS MATERIAL IMPREGNATED BY REACTIVE PULTRUSION |
| FR3121680B1 (en) | 2021-04-08 | 2024-04-12 | Arkema France | FLAME-RETARDANT POLYAMIDE COMPOSITIONS, THEIR USES AND PREPARATION PROCESSES |
| FR3121681A1 (en) | 2021-04-08 | 2022-10-14 | Arkema France | FLAME RETARDANT POLYAMIDE COMPOSITIONS, THEIR USES AND THEIR METHODS OF PREPARING THEM |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4291152A (en) * | 1979-03-27 | 1981-09-22 | Teijin Limited | Process for producing aromatic polyesters having increased degrees of polymerization |
| FR2694008B1 (en) * | 1992-07-24 | 1994-10-21 | Atochem Elf Sa | Polymers and copolymers resulting from the addition of oligomers with di-amino and di-hydroxy endings and bisoxazinones or bisoxazolinones, and their process for obtaining. |
| FR2694009B1 (en) * | 1992-07-24 | 1994-10-21 | Atochem Elf Sa | Polymers and copolymers resulting from the addition of oligomers with di-carboxy endings and bisoxazines or bisoxazolines, and their process for obtaining. |
-
1995
- 1995-04-27 FR FR9505061A patent/FR2733757B1/en not_active Expired - Fee Related
-
1996
- 1996-04-26 KR KR1019960013245A patent/KR960037721A/en not_active Application Discontinuation
- 1996-04-26 CA CA002175151A patent/CA2175151A1/en not_active Abandoned
- 1996-04-26 EP EP96400901A patent/EP0739924A1/en not_active Withdrawn
- 1996-04-26 CN CN96108420A patent/CN1141930A/en active Pending
- 1996-04-30 JP JP8132662A patent/JPH08337649A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1141930A (en) | 1997-02-05 |
| FR2733757B1 (en) | 1997-06-20 |
| JPH08337649A (en) | 1996-12-24 |
| FR2733757A1 (en) | 1996-11-08 |
| KR960037721A (en) | 1996-11-19 |
| EP0739924A1 (en) | 1996-10-30 |
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