CN1814649A - Nylon copolymer containing imidazole salt - Google Patents

Nylon copolymer containing imidazole salt Download PDF

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CN1814649A
CN1814649A CN 200510005284 CN200510005284A CN1814649A CN 1814649 A CN1814649 A CN 1814649A CN 200510005284 CN200510005284 CN 200510005284 CN 200510005284 A CN200510005284 A CN 200510005284A CN 1814649 A CN1814649 A CN 1814649A
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monomer
imidazole salts
nylon copolymer
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CN100467514C (en
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魏腾芳
何文岳
许智伟
刘瑞珍
叶诚
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Industrial Technology Research Institute ITRI
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Abstract

This invention relates to a nylon copolymer containing imidazole copolymerized by imidazole comonomers with dicarboxyl and comonomers of the groups selected from R to the power 6-O2C-R to the power 5-CO2R to the power 6, H2N-R to the power 7-CO2R to the power 8, H2N-R to the power 9-NH2, in which, the imidazolium is placed at the main chain of said copolymer since its dicarboxyl takes part in the polymerization reaction.

Description

The nylon copolymer that contains imidazole salts
Technical field
The relevant a kind of co-polymer that contains the aromatic series amine salt of the present invention particularly contains imidazole salts monomeric polymeric amide (Polyamide altogether; Be commonly called as nylon nylon) co-polymer, the characteristic that can be applicable to promote static resistance, wetting ability and the high fastness of dyeing of fabric or film product.
Background technology
The compound that the chemical structure of using quarternary ammonium salt arranged at present with polymkeric substance (for example, polyolefine, polyacrylic resin, polyethers etc.) copolymerization with spinning as fabric, the characteristic of static resistance, wetting ability and the high fastness of dyeing of increase fiber.But the quarternary ammonium salt heat-resisting durability be difficult to surpass 200 ℃, so can't be applied to that more high temperature is with the polymeric amide or the polyester of melt-spinning, imidazole salts (imidazolium salt) then can remedy above-mentioned shortcoming.Heat-resisting, anti-combustion that imidazole salts has, high dielectric substance, low-steam pressure and the advantage harmless relatively to human body are so promptly begin to be used in flux or Application of Catalyst field very early.More existing documents link imidazole salts with chemical bonded refractory and polymkeric substance, with its materialization and the applicability of increasing, for example United States Patent (USP) the 6th, 025, and No. 457 (2000 Christian eras) discloses a kind of main chain is polyolefine, and contains the co-polymer of imidazole salts at side chain.Electrochimica reports then among 2001,46,1407 (H.Ohno) that a kind of main chain is polyolefine or polyacrylic ester and side chain is the polyether polymer that terminal group contains imidazole salts.Contain imidazole salts monomeric polyethylene terephthalate copolymer compound altogether on TaiWan, China patent case number 197127 a kind of its main chains of report.But at present as yet not relevant for containing the imidazole salts report of monomeric polymeric amide co-polymer altogether on the main chain.
Summary of the invention
In view of above-mentioned, the purpose of this invention is to provide a kind of co-polymer that contains imidazole salts, in detail, the invention provides a kind of positive imidazol ion that on main chain, contains as being total to monomeric polymeric amide co-polymer.Nylon copolymer heat-resisting durability of the present invention is good, can be convenient to be applied to melt-spinning, and makes co-polymer make product that the characteristic of good static resistance, wetting ability and high fastness of dyeing can be arranged because of the characteristic of the imidazole salts that had.For reaching above-mentioned purpose, the co-polymer that contains imidazole salts of the present invention, by comprising following common monomer polymerization gained, wherein molar percentage is for the monomer of full entry chemical reaction.
(a) the common monomer of the formula of 0.1 mole of % to 50 mole of % (I):
In the formula, R 1And R 10Independently be-(CH 2) a-or its isomer, a is 1 to 20 integer.R 2, R 3, and R 4Then independent is H or C 1-21Alkyl.X is F, Cl, Br, I, RSO 3, RCO 2, BF 4, PF 6Or N (SO 3CF 3) 2, wherein each R is the independent C that is 1-5Alkane phenyl or C 1-5Alkyl.Y is-COOH.
(b) 50 moles of % to 99.9 mole of %'s selects from R 6-O 2C-R 5-CO 2R 6, H 2N-R 7-CO 2R 8, H 2N-R 9-NH 2And the common monomer of group that combination is formed.In the formula, R 5For phenyl, naphthyl, xenyl or-(CH 2) b-and isomer, b is 1 to 20 integer.R 7For phenyl, naphthyl, xenyl or-(CH 2) c-and isomer, c is 1 to 20 integer.R 6Be hydrogen or C 1-7Alkyl.R 8Be hydrogen or C 1-7Alkyl.R 9For-(CH 2) t-or its isomer, t is 1 to 40 integer.
Wherein, in above-mentioned (a) and the common monomer (b), its carboxyl is preferably 1: 1 with the ratio of amino.
Preferred a is 2 to 4 integer in the foregoing invention; R 2, R 3, and R 4Independent is H or C 1Alkyl; X is BF 4, PF 6Or N (SO 3CF 3) 2Y is-COOH; And R 5For-(CH 2) b-, b is 4; R 7For-(CH 2) c-, c is 5; R 6Be hydrogen or C 1-4Alkyl; R 9For-(CH 2) t-, t is 6.
Above-mentioned polyreaction is to carry out under a solvent-free state, and its polymerization temperature is between 160-260 ℃, and the time is 6-20 hour.
Above-mentioned polyreaction is to carry out under a solvent state, and its polymerization temperature is between 60-200 ℃, and the time is 6-30 hour; Wherein above-mentioned solvent is to comprise N-methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE or solion, and above-mentioned solion then has following chemical formula:
Figure A20051000528400071
Wherein, R 11And R 12Be the independent C that is 1-4Alkyl, X is PF 6Above-mentioned nylon copolymer comprises by following common monomer institute's copolymerization and getting: (a) 0.1 mole of % to 50 mole of %
Monomer altogether: and (b) 99.9 moles of % to 50 mole of % select from
Figure A20051000528400073
With Be total to the common monomer of monomer and group that combination is formed thereof; In wherein above-mentioned (a) and the common monomer (b), carboxyl is 1: 1 with the ratio of amino.
Above-mentioned nylon copolymer also comprises by following common monomer institute's copolymerization and getting: (a) 0.1 mole of % to 50 mole of %
Figure A20051000528400075
Be total to monomer; And (b) 99.9 moles of % to 50 mole of % hexanolactam with
Figure A20051000528400076
Be total to monomer; In wherein above-mentioned (a) and the common monomer (b), carboxyl is 1: 1 with the ratio of amino.
The above-mentioned nylon copolymer that contains imidazole salts is to have moisture regain on the whole to be 4.5%-5.5%.
The above-mentioned nylon copolymer that contains imidazole salts is that to have static resistance be 106-108 Ω cm.
The above-mentioned nylon copolymer that contains imidazole salts is after washing 50 times, and its washing fastness is greater than 4 grades.
Among the present invention, the imidazole salts structure can be heat-resisting 200 ℃, even more than 250 ℃, the co-polymer of itself and nylon can nylon required greater than 200 ℃ melt temperature under carry out melt-spinning or processing, the imidazole salts structure can be do not destroyed, the effect that it gives fiber or fabric can be possessed.In addition, can have moisture regain with prepared fabric of the present invention or film is 4.7%-5.5%, static resistance 106-108 Ω cm, and after having washing 50 times, and washing fastness is greater than 4 grades characteristic.
The co-polymer that contains imidazole salts of the present invention can be further has different effects according to the content of imidazole salts with the different of functional group or negative ion group, for example:
1. according to the number of imidazole salts content, can be applicable to anti-electrostatic polymer and fabric field.For example when imidazole salts content when 10 moles of % are above, its static resistance can reach 106 Ω cm.
2. have high moisture regain function, can be applicable to the wetting ability product development.
3. the negative ion group on the imidazole salts can be replaced by other compound with negative ion functional group, the broad Application Areas that provides post-treatment to handle.
4. with anionic dyestuff, when dyeing, wash 50 times after, washing fastness has the characteristic that significantly improves fastness of dyeing greater than 4 grades.
Embodiment
The co-polymer that contains imidazole salts of the present invention comprises by common monomer institute's copolymerization of following (a) and (b) getting.
(a) 0.1 mole of % to 50 mole of % is preferably 2 moles of % to 15 mole of %, and is more preferred from the common monomer of the formula (I) of 5 moles of % to 7 mole of %:
Figure A20051000528400081
In the formula, R 1And R 10Independently be-(CH 2) a-or its isomer, a is 1 to 20, is preferably 1 to 8 integer.That is R, 1And R 10Can independently be one to have 1 to 20, be preferably the straight or branched alkyl of 1 to 8 carbon atom.R 1And R 10When the phase XOR was identical, the co-polymer that contains imidazole salts of the present invention all can reach the effect of being desired, and works as R 1And R 10When identical, the convenience on synthesizing is arranged.
R 2, R 3, and R 4Can independently be H or C 1-21The straight or branched alkyl, be preferably H or C 1-6The straight or branched alkyl.
X is F, Cl, Br, I, RSO 3, RCO 2, BF 4, PF 6Or N (SO 3CF 3) 2, wherein each R is the independent C that is 1-5Alkane phenyl or C 1-5Alkyl.Therefore, X-is the relative negative ion of positive imidazol ion.
Y is-COOH, the functional group who uses as copolymerization.
Therefore, herein about the positive ion of imidazole salts compound used in the present invention (formula (I)), be on positive imidazol ion (imidazolium) molecular grouping (moiety), having two carboxyl persons, that is have the imdazole derivatives of two carboxyls.
(b) 99.9 moles of % to 50 mole of % are preferably 98 moles of % to 85 mole of %, and are more preferred from the selecting from R of 95 moles of % to 93 mole of % 6-O 2C-R 5-CO 2R 6, H 2N-R 7-CO 2R 8, H 2N-R 9-NH 2, and the common monomer of group that combination is formed.In the formula, R 5For phenyl, naphthyl, xenyl or-(CH 2) b-and isomer, b is 1 to 20, is preferably 1 to 8 integer.R 7For phenyl, naphthyl, xenyl or-(CH 2) c-and isomer, c is 1 to 20, is preferably 1 to 10 integer.R 6Be hydrogen or C 1-7Alkyl, and be preferably hydrogen or C 1-4Alkyl.R 8Be hydrogen or C 1-7Alkyl, and be preferably hydrogen or C 1-4Alkyl.R 9For-(CH 2) t-or its isomer, t is 1 to 40, is preferably 1 to 12 integer.
Wherein, in above-mentioned (a) and the common monomer (b), its carboxyl is preferably 1: 1 with the ratio of amino.
Above-mentioned altogether monomeric polyreaction is to carry out under solvent-free state, and wherein polymerization temperature is between 160~260 ℃, and the reaction times is 6-20 hour.In addition, polyreaction also can be carried out under the solvent state, wherein above-mentioned solvent can be N-Methyl pyrrolidone (NMP), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc) and solion (ionic solvent) etc., its polymerization temperature is between 60~200 ℃, and the reaction times is 6-30 hour.
Above-mentioned solion can have following chemical formula:
Figure A20051000528400101
Wherein, R 11And R 12Be the independent C that is 1-4Alkyl.X is PF 6
When making the co-polymer that contains imidazole salts of the present invention, at first imidazole derivative is carried out upgrading, make to be formed on the imidazole ring positively chargedly and have two and be the salt of carboxylic acid substituent endways, promptly be total to monomer (a).The monomer (monomer (b) altogether) that will be total to monomer (a) and nylon carries out polyreaction with the general method of making nylon, the positive imidazol ion that makes imidazole salt participates in polyreaction with its dicarboxyl and is positioned on the main chain of formed co-polymer, can obtain the co-polymer that contains imidazole salts of the present invention.Can have the characteristic of static resistance, wetting ability and high fastness of dyeing with prepared fabric of co-polymer or the film that contains imidazole salts of the present invention.
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, be described in detail below:
Embodiment
Synthesis example: imidazoles monomer (compound 2, compound 2a and compound 2b) synthetic with dicarboxyl
Synthesizing of compound 2:
At first, the present invention can utilize chloride imidazoles monomer reaction (compound 1) that following formula has a dicarboxyl in acetone solvent down and KPF 6Carry out anionic exchange, then can obtain with PF 6Be anionic dicarboxyl imidazole salts compound (consulting following flow process).
Figure A20051000528400102
Potassium Hexafluorophosphate (KPF with 55 grams (0.30mol) 6) add and contain in 500 milliliters the acetone soln of 50 g of (0.23mol) compounds 1, and under room temperature, stirred five days.Reaction soln is filtered, and behind the concentrated filtrate, get final product the compound 2 of oily product.
The SPECTRAL DATA 1H NMR of compound 2 (d6-DMSO, 200MHz):
δ8.85(1H),7.56(2H),4.39(4H),3.67(4H),2.16(4H)。
Compound 2a's is synthetic:
Identical with the synthetic method of compound 2, but wherein be with potassium tetrafluoroborate KBF 4(37.8g 0.30mol) substitutes Potassium Hexafluorophosphate (KPF 6).
Compound 2b's is synthetic:
Identical with the synthetic method of compound 2, but with two trifluoro sulfanilamide (SN) KN (SO 2CF 3) 2(95.7g 0.30mol) substitutes Potassium Hexafluorophosphate (KPF 6).
Figure A20051000528400112
Embodiment 1: contain the manufacturing of nylon 66 co-polymers (compound 5) of hexafluorophosphate imidazoles monomer (compound 2)
The phosphofluoric acid imidazoles monomer (compound 2) with dicarboxyl that utilizes above-mentioned synthesis example 1 to be obtained carries out the manufacturing that contains imidazole salts nylon 66 co-polymers of the present invention.Nylon 66 is by 1,6-hexanediamine and 1, and the 6-hexanodioic acid dewaters polymerization and gets, because used amine and acid respectively contains six carbon atom, thereby this kind polymkeric substance spy is called nylon 66.Forming the present invention, to contain the reaction formula of nylon 66 co-polymers of imidazole salts as follows:
Get the di adipate monomer (compound 3) of 33 the hexafluorophosphate imidazoles monomers (compound 2) that obtained of gram (0.1mol) synthesis examples 1 and 78 grams (0.4mol) with dicarboxyl, and 58 the gram (0.5mol) hexanediamine monomer (compound 4) mix after, stirred 30 minutes down in 110 ℃, after then adding the tributyl tin (TBT) of 0.3 gram (1000ppm), be warming up to 270 ℃ gradually and stirred 3 hours, leave standstill cooling.The ethyl acetate of adding 100 grams are cleaned, and are then centrifugal with the water of 100 grams, carry out sedimentation in the methyl alcohol of water intaking soluble layer adding 500 grams, can obtain white solid product (compound 5), the co-polymer that contains imidazole salts promptly of the present invention.
Reaction finish purified after, can determine the carrying out of polyreaction by 1H NMR, the decomposition temperature of this polymer product (Td) is 337.0 ℃, and when being heated to 450 ℃, its cracking 17.1%, melting temperature (Tm) is 257 ℃, crystallisation by cooling temperature (Tcc) is 178.2 ℃.Utilization is that the colloid of standardized solution penetrates chromatography (gel permeation chromatography with polystyrene (polystyrene); GPC) weight average molecular weight (MW) of measurement polymer product (compound 5) is 25,000.In this polymer product, its imidazoles monomer: the monomeric theoretical value of di adipate is 1.0: 4.0, and calculates the imidazoles monomer of gained via NMR spectrum: the di adipate monomer is 1.00: 3.95.
The SPECTRAL DATA 1H NMR (CF of compound 5 3COOD, 200MHz):
δ9.08,7.78,4.63,4.45,4.17,2.69,2.20,1.85。
FT-IR:3436,1715,1463,1203,1127,1028cm -1
Embodiment 2: contain the manufacturing of nylon 66 co-polymers (compound 5a) of a tetrafluoro borate imidazoles monomer (compound 2a)
Identical with the synthetic method of embodiment 1, but substitute hexafluorophosphate imidazoles monomer (compound 2) with a tetrafluoro borate imidazoles monomer (compound 2a) 27.3 grams (0.1mol), obtain nylon 66 co-polymers (compound 5a), its decomposition temperature (Td) is 330 ℃, then cracking 22% when being heated to 450 ℃, melting temperature (Tm) is 251 ℃.
Figure A20051000528400121
Embodiment 3: contain the manufacturing of nylon 6 co-polymers (compound 7) of hexafluorophosphate imidazoles monomer (compound 2).
The phosphofluoric acid imidazoles monomer (compound 2) with dicarboxyl that utilizes above-mentioned synthesis example 1 to be obtained carries out the manufacturing that contains imidazole salts nylon 6 co-polymers of the present invention.Nylon 6 be by the hexanolactam of six carbon numbers (Caprolactam) through the polymkeric substance that open loop was polymerized, thereby this kind polymkeric substance spy is called nylon 6.Forming the present invention, to contain the reaction formula of nylon 6 co-polymers of imidazole salts as follows:
Figure A20051000528400131
Get the hexanolactam (compound 6) of 33 the phosphofluoric acid imidazoles monomers (compound 2) that obtained of gram (0.1mol) synthesis examples 1 and 113 grams (1.0mol) with dicarboxyl, and 11.6 the gram (0.1mol) hexanediamine monomer (compound 4) mix after, stirred 30 minutes down in 110 ℃, after then adding the tributyl tin (TBT) of 0.3 gram (1000ppm), be warming up to 250 ℃ gradually and stirred 3 hours, leave standstill cooling.The ethyl acetate of adding 100 grams are cleaned, and are then centrifugal with the water of 100 grams, carry out sedimentation in the methyl alcohol of water intaking soluble layer adding 500 grams, can obtain white solid product (compound 7), that is the co-polymer that contains imidazole salts of the present invention.
Reaction finish purified after, can determine the carrying out of polyreaction by 1H NMR, the decomposition temperature of this polymer product (Td) is 310.0 ℃, and when being heated to 450 ℃, its cracking 27.0%, melting temperature (Tm) is 201 ℃, crystallisation by cooling temperature (Tcc) is 164.2 ℃.Utilization is that the colloid of standardized solution penetrates chromatography (gel permeation chromatography with polystyrene (polystyrene); GPC) weight average molecular weight (MW) of measurement polymer product (compound 7) is 23,000.Imidazoles monomer in this polymer product: the monomeric theoretical value of di adipate is 1.0: 10.0, and calculates the imidazoles monomer of gained via NMR spectrum: the di adipate monomer is 1.0: 9.7.
The SPECTRAL DATA 1H NMR (CF of compound 7 3COOD, 200MHz):
δ9.08,7.8,4.63,4.5,4.13,2.71,2.20,1.81。
FT-IR:3432,1712,1463,1200,1120,1022cm -1
Embodiment 4: contain the manufacturing of nylon 6 co-polymers (compound 7a) of a tetrafluoro borate imidazoles monomer (compound 2a)
Identical with the synthetic method of embodiment 3, but substitute hexafluorophosphate imidazoles monomer (compound 2) with a tetrafluoro borate imidazoles monomer (compound 2a) 27.3 grams (0.1mol), obtain nylon 6 co-polymers (compound 7a), its decomposition temperature (Td) is 300 ℃, then cracking 30% when being heated to 450 ℃, melting temperature (Tm) is 197 ℃.
Figure A20051000528400141
Embodiment 5: contain two trifluoro sulfanilamide (SN) salt N (SO 2CF 3) 2The manufacturing of nylon 6 co-polymers (compound 7b) of monomer (compound 2b)
Identical with the synthetic method of embodiment 3, but to contain two trifluoro sulfanilamide (SN) salt N (SO 2CF 3) 2Monomer (compound 2b) 46.6g (0.1mol) substitutes hexafluorophosphate imidazoles monomer (compound 2), obtain nylon 6 co-polymers (compound 7b), its decomposition temperature (Td) is 315 ℃, then cracking 14% when being heated to 450 ℃, and melting temperature (Tm) is 199 ℃.
Figure A20051000528400142
The SPECTRAL DATA 1H NMR (CF of compound 7b 3COOD, 200MHz):
δ9.0,S.1,4.7,4.4,4.2,2.3,2.2,1.9。
FT-IR:3442,1718,1467,1200,1125,1020cm -1
Embodiment 6: contain the manufacturing of nylon 6 co-polymers in solion of imidazole salts
The nylon copolymer that the present invention contains imidazole salts is can be in for example making in NMP, DMF, DMAc and the solion equal solvent, and present embodiment is to carry out the manufacturing that the present invention contains nylon 6 co-polymers of imidazole salts, wherein R in the solion of following formula 11Be methyl, R 12Be butyl, X is PF 6
Figure A20051000528400151
Get the hexanolactam (compound 6) of 33 the phosphofluoric acid imidazoles monomers (compound 2) that obtained of gram (0.1mol) synthesis examples 1 and 113 grams (1.0mol) with dicarboxyl, and mix in solion 30 grams of hexanediamine monomer (compound 4) the adding following formula of 11.6 grams (0.1mol), stirred 30 minutes down in 110 ℃, after then adding the tributyl tin (TBT) of 0.3 gram (1000ppm), be warming up to 160 ℃ gradually and stirred 26 hours, leave standstill cooling.The ethyl acetate that adds 100 grams is cleaned, then centrifugal with the water of 100 grams, carry out sedimentation in the methyl alcohol of water intaking soluble layer adding 500 grams, can obtain white solid product (compound 7), that is the co-polymer that contains imidazole salts of the present invention's manufacturing in solion.
Reaction finish purified after, can determine the carrying out of polyreaction by 1H NMR, the decomposition temperature of this polymer product (Td) is 330.0 ℃, and when being heated to 450 ℃, its cracking 16.0%, melt temperature (Tm) is 205 ℃, crystallisation by cooling temperature (Tcc) is 169 ℃.Utilization is that the colloid of standardized solution penetrates chromatography (gelpermeation chromatography with polystyrene (polystyrene); GPC) weight average molecular weight (MW) of measurement polymer product (compound 7) is 28,000.Imidazoles monomer in this polymer product: the monomeric theoretical value of di adipate is 1.0: 10.0, and calculates the imidazoles monomer of gained via NMR spectrum: the di adipate monomer is 1.0: 9.7.
Spectroscopic data 1HNMR (the D of institute's synthetic compound 7 in the solution of solion 2O, 200MHz):
δ9.08,7.8,4.63,4.5,4.13,2.71,2.20,1.81。
FT-IR:3432,1712,1463,1200,1120,1022cm -1
The moisture regain of polymkeric substance, static resistance and chromatic test result:
Polymeric amide co-polymer film to embodiment of the invention 1-5 carries out moisture regain, static resistance and chromatic test.
Test case 1 (antistatic test):
With embodiment 2 and embodiment 4 contain the monomeric nylon 66 of a tetrafluoro borate imidazoles and nylon 6 co-polymers (compound 5a and compound 7a) are made film respectively, area is 20mm * 40mm, is positioned in 100 ℃ of baking ovens oven dry 10 hours.The resistance value testing tool is a low voltage four-point resistance value tester, and 0.001 ampere of fixed current (IS) measures its voltage (Vm), and each test piece measures sheet resistance 20 times, at last with n ~ = ( Πt / ln 2 ) ( VM / I S ) Conversion resistance.Compound 5a and compound 7a are that to record resistance value respectively be 2 * 10 8Ω cm and 3 * 10 7Ω cm; Then be respectively 7 * 10 with nylon 66 and the measured resistance value of nylon 6 experiment in contrast 9Ω cm and 5 * 10 8Ω cm.
Test case 2 (moisture regain test):
Make film respectively with containing monomeric nylon 66 of a tetrafluoro borate imidazoles and nylon 6 co-polymers (compound 5a and compound 7a) among embodiment 2 and the embodiment 4, area is 20mm * 40mm, is positioned in 100 ℃ of baking ovens to dry 10 hours.Place 23 ℃ then, under the condition of 65RH%, the weight of measured its increase (suction) is respectively 4.9% and 5.3% after 24 hours, and the hygroscopicity value of testing in contrast with nylon 66 and nylon 6 then is respectively 4.0% and 4.2%.
Test case 3 (stain test):
The co-polymer of embodiment 1-5 is made film according to the mode of test case 1 respectively, in about 98 ℃ aqueous solution, add anionic dyestuff, carry out stain test, after about 30 minutes, soap.After washing 50 times, its washing fastness is greater than 4 grades, and be the experiment of contrast with nylon 66 and nylon 6, and after washing 20 times, it washes fastness then less than 4 grades.
Though the present invention discloses as above with preferred embodiment, so it is not in order to limit the present invention.Anyly be familiar with this skill person, without departing from the spirit and scope of the present invention, when doing a little change and retouching.Therefore protection scope of the present invention is as the criterion when looking the scope that accompanying Claim defines.

Claims (9)

1, a kind of nylon copolymer that contains imidazole salts is characterized in that by comprising following common monomer polymerization gained:
(a) the common monomer of the formula of 0.1 mole of % to 50 mole of % (I):
In the formula, R 1And R 10Independently be-(CH 2) a-or its isomer, a is 1 to 20 integer, R 2, R 3, and R 4Then independent is H or C 1-21Alkyl, X is F, Cl, Br, I, RSO 3, RCO 2, BF 4, PF 6Or N (SO 3CF 3) 2, wherein each R is the independent C that is 1-5Alkane phenyl or C 1-5Alkyl, Y is-COOH; And
(b) 50 moles of % to 99.9 mole of %'s selects from R 6-O 2C-R 5-CO 2R 6, H 2N-R 7-CO 2R 8, H 2N-R 9-NH 2And the common monomer of group that combination is formed;
In the formula, R 5For phenyl, naphthyl, xenyl or-(CH 2) b-and isomer, b is 1 to 20 integer; R 7For phenyl, naphthyl, xenyl or-(CH 2) c-and isomer, c is 1 to 20 integer; R 6Be hydrogen or C 1-7Alkyl, R 8Be hydrogen or C 1-7Alkyl; R 9For-(CH 2) t-or its isomer, t is 1 to 40 integer;
In wherein above-mentioned (a) and the common monomer (b), its carboxyl is 1: 1 with the ratio of amino,
Wherein molar percentage is for the monomer of full entry chemical reaction.
2, the nylon copolymer that contains imidazole salts according to claim 1 is characterized in that a is 2 to 4 integer; R 2, R 3, and R 4Independent is H or C 1Alkyl; X is BF 4, PF 6Or N (SO 3CF 3) 2Y is-COOH; And R 5For-(CH 2) b-, b is 4; R 7For-(CH 2) c-, c is 5; R 6Be hydrogen or C 1-4Alkyl; R 9For-(CH 2) t-, t is 6.
3, the nylon copolymer that contains imidazole salts according to claim 1 is characterized in that above-mentioned polyreaction is to carry out under a solvent-free state, its polymerization temperature is between 160-260 ℃, and the time is 6-20 hour.
4, the nylon copolymer that contains imidazole salts according to claim 1 is characterized in that above-mentioned polyreaction is to carry out under a solvent state, its polymerization temperature is between 60-200 ℃, and the time is 6-30 hour; Wherein above-mentioned solvent is to comprise N-methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE or solion, and above-mentioned solion then has following chemical formula:
Wherein, R 11And R 12Be the independent C that is 1-4Alkyl, X is PF 6
5, the nylon copolymer that contains imidazole salts according to claim 1 is characterized in that comprising by following common monomer institute's copolymerization getting:
(a) 0.1 mole of % to 50 mole of %
Figure A2005100052840003C2
Be total to monomer; And
(b) 99.9 moles of % to 50 mole of %'s selects certainly
Figure A2005100052840003C3
With Be total to the common monomer of monomer and group that combination is formed thereof;
In wherein above-mentioned (a) and the common monomer (b), carboxyl is 1: 1 with the ratio of amino.
6, the nylon copolymer that contains imidazole salts according to claim 1 is characterized in that comprising by following common monomer institute's copolymerization getting:
(a) 0.1 mole of % to 50 mole of % Be total to monomer; And
(b) hexanolactam of 99.9 moles of % to 50 mole of % with
Figure A2005100052840003C6
Be total to monomer;
In wherein above-mentioned (a) and the common monomer (b), carboxyl is 1: 1 with the ratio of amino.
7, the nylon copolymer that contains imidazole salts according to claim 1 is characterized in that the above-mentioned nylon copolymer that contains imidazole salts is that to have moisture regain be 4.5%-5.5%.
8, the nylon copolymer that contains imidazole salts according to claim 1 is characterized in that the above-mentioned nylon copolymer that contains imidazole salts is that to have static resistance be 106-108 Ω cm.
9, the nylon copolymer that contains imidazole salts according to claim 1 is characterized in that the above-mentioned nylon copolymer that contains imidazole salts after washing 50 times, and its washing fastness is greater than 4 grades.
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