TWI295674B - Imidazolium-based nylon copolymer - Google Patents
Imidazolium-based nylon copolymer Download PDFInfo
- Publication number
- TWI295674B TWI295674B TW93140981A TW93140981A TWI295674B TW I295674 B TWI295674 B TW I295674B TW 93140981 A TW93140981 A TW 93140981A TW 93140981 A TW93140981 A TW 93140981A TW I295674 B TWI295674 B TW I295674B
- Authority
- TW
- Taiwan
- Prior art keywords
- mol
- compound
- group
- nylon
- salt
- Prior art date
Links
- 239000004687 Nylon copolymer Substances 0.000 title claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 title claims description 4
- 239000000178 monomer Substances 0.000 claims description 38
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 16
- 150000002460 imidazoles Chemical class 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 150000004693 imidazolium salts Chemical class 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000004677 Nylon Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 241000238413 Octopus Species 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- 150000002923 oximes Chemical class 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- -1 aromatic amine salt Chemical class 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 22
- 229940125782 compound 2 Drugs 0.000 description 16
- 229920000642 polymer Chemical class 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 14
- 229920002302 Nylon 6,6 Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229920000393 Nylon 6/6T Polymers 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229940125898 compound 5 Drugs 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 6
- VUDZSIYXZUYWSC-DBRKOABJSA-N (4r)-1-[(2r,4r,5r)-3,3-difluoro-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-4-hydroxy-1,3-diazinan-2-one Chemical compound FC1(F)[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)N[C@H](O)CC1 VUDZSIYXZUYWSC-DBRKOABJSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 4
- 150000001450 anions Chemical group 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- SHAHPWSYJFYMRX-GDLCADMTSA-N (2S)-2-(4-{[(1R,2S)-2-hydroxycyclopentyl]methyl}phenyl)propanoic acid Chemical compound C1=CC([C@@H](C(O)=O)C)=CC=C1C[C@@H]1[C@@H](O)CCC1 SHAHPWSYJFYMRX-GDLCADMTSA-N 0.000 description 3
- LDIOUQIXNSSOGU-UHFFFAOYSA-N 8-(3-pentylamino)-2-methyl-3-(2-chloro-4-methoxyphenyl)-6,7-dihydro-5h-cyclopenta[d]pyrazolo[1,5-a]pyrimidine Chemical compound CC1=NN2C(NC(CC)CC)=C3CCCC3=NC2=C1C1=CC=C(OC)C=C1Cl LDIOUQIXNSSOGU-UHFFFAOYSA-N 0.000 description 3
- 229910021135 KPF6 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 3
- 101100328518 Caenorhabditis elegans cnt-1 gene Proteins 0.000 description 2
- 235000015429 Mirabilis expansa Nutrition 0.000 description 2
- 244000294411 Mirabilis expansa Species 0.000 description 2
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229930182558 Sterol Natural products 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000013536 miso Nutrition 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 150000003432 sterols Chemical class 0.000 description 2
- 235000003702 sterols Nutrition 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- VYMRUHYACWVUTM-UHFFFAOYSA-N 2,2,4,4,5,5-hexafluoroimidazolidine Chemical compound FC1(NC(C(N1)(F)F)(F)F)F VYMRUHYACWVUTM-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 229920003188 Nylon 3 Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 210000000003 hoof Anatomy 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
Landscapes
- Polyamides (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
1295674 九、發明說明： 【發明所屬之技術領域】 本發明有關一種含芳香族胺鹽之共聚合物，特別是含咪唑 鹽共單體之聚醯胺（Polyamide;俗稱尼龍nyi〇n)*聚合物，可應 用於增進織物或薄膜產品之抗靜電性、親水性以及高染色監牢 度之特性。 ^ 【先前技術】 目前有使用四級銨鹽之化學結構的化合物與聚合物（例 如’聚稀烴、聚丙烯酸樹月旨、聚醚等）共聚合以紡絲做為纖維織 物’增加纖維之抗靜電性、親水性以及高染色監牢度之特性。 但是四級铵鹽耐熱持久性很難超過挪。c，所以無法應用於需 要更高溫㈣融紡絲之聚醯胺或« ,而㈣鹽（imidazolium salt)則可彌補上述缺點。咪唑鹽具有耐熱、耐燃、高介電質、 低蒸汽塵及對人體相對·盔宝夕彳尾奶从#曰θ 、 . 和耵無害之優點，故很早即開始被使用於熔 劑或催化劑之應用領域。6有—些文獻將咪㈣以化學鍵结血 聚合物連結’關增其物化性及應錄，例如美國專利第 6,025,457 號（西元 2〇〇〇 车、据一 ^ ^ 年）揭不一種主鏈為聚烯烴，而在 含㈣之共聚合物，伽—細，4一 中則報告-種主鏈為聚烯煙或聚丙稀_而侧鏈 唑鹽之聚醚聚合物。中華民土 3本 τ芈民國專利案唬ϊ97127則報告一 鏈上含咪唑鹽共單體之肀而匕u取人w ^ 鏈上含呼…：：共聚合物。但是目前尚未有關於主 键上含μ鹽共早體之聚醯胺共聚合物之報導。 【發明内容】 鑑於上述， 本發明之目的隸供-種含“鹽之共聚合 1295674 物，詳言之，本發明提供一種在主 單體之聚醢胺共聚合物。本發明之尼龍3共聚:::::為共 絲’並使共聚合物能因_= ::特1·生而使產品能有良好之抗靜電性、親水性 牛度之特性。為達成上述目的，本發明之含㈣鹽之^^ 由包括下列之共單體聚合所得： ，、眾口物， ⑷〇·1莫耳。)至50莫耳％之式⑴之共單體·· R4 Y-R1·1295674 IX. Description of the Invention: [Technical Field] The present invention relates to a copolymer containing an aromatic amine salt, particularly a polyamide containing an imidazolium salt comonomer (Polyamide; commonly known as nylon nyi〇n)* polymerization. It can be used to improve the antistatic properties, hydrophilicity and high dyeing fastness of fabric or film products. ^ [Prior Art] There are currently compounds which use a chemical structure of a quaternary ammonium salt and a polymer (for example, 'polycarbonate, polyacrylic acid, polyether, etc.) to be spun as a fiber fabric. Antistatic, hydrophilic and high dyeing fastness properties. However, the durability of the quaternary ammonium salt is hard to exceed. c, so it cannot be applied to polyamine or «, which is required to melt at a higher temperature (4), and the imidazolium salt can make up for the above disadvantages. The imidazole salt has the advantages of heat resistance, flame resistance, high dielectric property, low vapor dust and harmlessness to the human body. It is harmless from #曰θ, . and 耵, so it has been used for flux or catalyst very early. Application area. 6 There are some documents that link the (4) chemically bonded blood polymer to 'Kuan Zeng's physicochemical properties and should be recorded. For example, US Patent No. 6,025,457 (No. 2 car, according to one ^ ^ year) does not reveal a main chain. It is a polyolefin, and in the copolymer containing (4), gamma-fine, 4-reports, the polyether polymer of the polyalkylene or polypropylene-side and the side chain azole salt is reported. The Chinese folk land 3 τ芈 Republic of China patent case 唬ϊ97127 reports that the chain contains imidazolium salt comonomer and 匕u takes the human w ^ chain containing the call...:: copolymer. However, there have been no reports on polyamine copolymers containing a mu-salt co-precipitate on the primary bond. SUMMARY OF THE INVENTION In view of the above, the object of the present invention is to provide a "salt-containing copolymerization of 1295756. In particular, the present invention provides a polyamine copolymer in a main monomer. The nylon 3 copolymer of the present invention ::::: is a conjugated wire' and enables the copolymer to have good antistatic properties and hydrophilicity as a result of _=::1. In order to achieve the above object, the present invention The salt containing (4) salt is obtained by polymerization of the following comonomers: ,, public mouth, (4) 〇·1 mol.) to 50 mol% of the comonomer of formula (1) · R4 Y-R1·
(I) 式中，R1及Ri()獨立為_(CH2)a_或其異構物，&為1至Ν 之整數。R2、R3、及R4則獨立為η、或c⑷之院基。又為卜(I) wherein R1 and Ri() are independently _(CH2)a_ or an isomer thereof, and & is an integer from 1 to Ν. R2, R3, and R4 are independently the base of η, or c(4). Again
C卜 Br、I、RS03、RC02、BF4、PF6 或 N(S03CF3)2，其中各 R 乃獨立為c】·5之烷苯基或Cu之烧基。γ a_COOH。 (b) 50 莫耳％至 99·9 莫耳。/。之擇自 R6_〇2C-R5_c〇2R6、 H2N_R7_C〇2R8、H2N-R9-NH2、及其組合所組成族群之共單體。 式中，R5為苯基、萘基、聯苯基、或-(CH2)b-及其異構物，b為 1至20之整數。R7為苯基、萘基、聯苯基、或_(CH2)e_及其異構 物，c為1至20之整數。R6為氫或Cw烷基。r8為氫或c] 7烷 基。R9為-(CH2)t-或其異構物，t為1至40之整數。 其中，上述（a)與（b)之共單體中，其羧基與胺基之比例較佳 為 1:1 〇 本發明中，咪唑鹽結構可耐熱200°c，甚至250°c以上，其 與尼龍之共聚合物可在尼龍所需之大於200°C之熔融溫度下進 行熔融紡絲或加工，不會破壞咪唑鹽結構，可保有其賦予纖維 1295674 ί:?二功效。。另，以本發明所製得之織物或薄膜可具有回潮 洗-次後，水洗堅牢度大於4級之特=A^，cm)’且具有水 ::明之含咪唑鹽之共聚合物可進一步依咪唑 s結或負離子基團之不同而具有不同之功效，.：1里與 1·依咪唑鹽含量^ ^ _ 物領域。例如當二ί在：=抗靜電聚合物及纖維織 達咖·cm。 里在10莫耳％以上時’其抗靜電性可 2·具有高回潮率功能’可應用於親水性產品開發。 合物:t鹽t之負離子基團可被其他具有負離子官能基之化 斤取代，提供後加工處理之寬廣應用領域。 於4級料’進行染色時，水洗50次後，水洗堅牢度大 、、、及，具有大幅提高染色堅牢度之特性。 【實施方式】 本毛明之含咪唑鹽之共聚合物，包括由下列 早體所共聚合而得。 、； ⑷G.1莫耳％至50莫耳％，較㈣2莫耳％至U莫耳％， 及更佳為5莫耳％至7莫耳％之式⑴之共單體： Y-R1·Cb Br, I, RS03, RC02, BF4, PF6 or N(S03CF3)2, wherein each R is independently an alkylphenyl group of c. γ a_COOH. (b) 50% to 99.9 Moher. /. The comonomers are selected from the group consisting of R6_〇2C-R5_c〇2R6, H2N_R7_C〇2R8, H2N-R9-NH2, and combinations thereof. In the formula, R5 is phenyl, naphthyl, biphenylyl or -(CH2)b- and an isomer thereof, and b is an integer of from 1 to 20. R7 is phenyl, naphthyl, biphenylyl, or _(CH2)e_ and an isomer thereof, and c is an integer of from 1 to 20. R6 is hydrogen or Cw alkyl. R8 is hydrogen or c] 7 alkyl. R9 is -(CH2)t- or an isomer thereof, and t is an integer from 1 to 40. Wherein, in the comonomers of the above (a) and (b), the ratio of the carboxyl group to the amine group is preferably 1:1. In the present invention, the imidazolium salt structure is heat-resistant to 200 ° C or even 250 ° C or more. The copolymer with nylon can be melt-spun or processed at a melting temperature of more than 200 ° C required for nylon without destroying the structure of the imidazole salt, and retains the effect of imparting 1,295,674 ί:? . In addition, the fabric or film obtained by the present invention may have a water-repellent fastness of more than 4 grades = A ^, cm)' and has water: the imidazole salt-containing copolymer may further It has different effects depending on the imidazole s junction or negative ion group, and the content of 1 :1 and imidazole salt ^ ^ _ in the field of matter. For example, when two ί is in: = antistatic polymer and fiber woven coffee · cm. When it is 10 mol% or more, its antistatic property can be 2. It has a high moisture regain function. It can be applied to the development of hydrophilic products. The anion group of the t salt t can be replaced by other cations having an anionic functional group, providing a wide range of applications for post processing. When dyeing is carried out in the fourth grade material, after washing 50 times, the washing fastness is large, and the dyeing fastness is greatly improved. [Embodiment] The imidazole salt-containing copolymer of the present invention includes the copolymerization of the following precursors. (4) G.1 mol% to 50 mol%, more than (4) 2 mol% to U mol%, and more preferably 5 mol% to 7 mol% of the formula (1) comonomer: Y-R1·
(I) 幸”土 ：中’R及Rl°獨立為_(CH2)a或其異構物，a為1至20， =7之整數，，R、R1。可獨立為一具有…。個， 1 永坐1之共聚合物均可達到所欲之功效， 1295674 而田R及R 0相同時，有合成上之便利性。 R、R3、及R4可獨立為Η、或Ci2i之直鏈或支鏈烷基， 圭為H'或Cl_6之直鏈或支鏈烧基。 X 為 F、C1、Br、ί、RS〇3、RC〇2、BF4、PF6 或 n(s〇3CF3)2， ’、中各R乃獨立為Ci·5之烧苯基或Cl·5之烷基。因此，x乃正 咪唑離子之相對負離子。 Y為-COOH，做為共聚合用之官能基。 因此，本文中關於本發明所使用之咪唑鹽化合物（式（I))之 正離子，乃為在正咪唑離子（imidazolium)分子團（moiety)上具有 二個羧基者，亦即具有二個羧基之咪唑衍生物。 (b)99.9莫耳％至50莫耳％，較佳為98莫耳％至85莫耳 及更佳為95莫耳％至93莫耳％之擇自r6-〇2C_r5_c〇2r6、 H2NR C02R、h2N-R9-NH2、及其組合所組成族群之共單體。 式中R為苯基、奈基、聯苯基、或_(CH2)b_及其異構物，b為 1至20，較料丨至8之整數。R7為苯基、萘基、聯苯基、或 -(CH2V及其異構物，c為！至2〇，較佳為i至1〇之整數。r6 為氫或c"燒基，而較佳為氫、或&烧基。r8為氯或c】^完 基，且較佳為氫、或Ci4絲。rU_(ch士或其異構物，t為 1至40，較佳為】至12之整數。 其中’上述⑷與⑻之共單體中，其羧基與胺基之比例較佳 上述共單體之聚合反應係可於無溶劑之狀態下 聚合溫度介於16〇〜26(TC ’而反應時間為6_2〇小時。另，聚人 反應亦可於溶劑狀態下進行，其中上述之溶劑^ 酮（NMP)、二甲基甲醯胺（dm T暴各烷 工'—个（、 ]—甲基乙醯胺（DMAc)以及離 子>谷液（1。*油_等，其聚合溫度介於6。〜2()代，反應時間 1295674 為6-30小時。 上述之離子溶液可I右 J丹有下列之化學式 義2 及b係獨立為C"之烷基。 在1造本發明之含咪唑鴎 生物進行改質’使形成在咪且::輸類衍 為羧酸取代基之鹽，即丑單雜，、T電何且具有二個在末端 單體\ (a)°將共單體⑷與尼龍之單體（共 味峻離子Λ 法騎聚妓應，使輕鹽類之正 ’、 —羧基參與聚合反應而位於所形成之J£聚人物的 主鏈上，即可鞾缉太於nR A ,〜风灰口物的 含畔唑蹄… 咪唑鹽之共聚合物。以本發明之 合物所製得之織物或薄膜可具有抗靜電性、親 水性以及南染色監牢度之特性。 為讓本發明之上述和其他目的、特徵、和優點能更明顯易 懂，下文特舉出較佳實施例，作詳細說明如下： 實施例 口成例· 有一緩基之味唾單趙（化合物2、化合物^以及化合 物2b)之合成 化合物2之合成·· 首先’本發明可利用下式具有二竣基之含氣味唾單體反應 (化合物1)於丙酮溶劑下與ΚΡΙ?6進行陰離子之交換，則可獲得 以PF6為陰離子之二缓基味。坐鹽化合物（參閱下列流程）。 1295674 H〇〇C^i0N^ 化合物1(I) Fortunately, "soil:" 'R and Rl° are independently _(CH2)a or its isomers, a is an integer from 1 to 20, = 7, and R, R1 can be independently one with .... , 1 永 坐 1 co-polymer can achieve the desired effect, 1295674 and R and R 0 are the same, there is a synthetic convenience. R, R3, and R4 can be independently Η, or Ci2i linear Or a branched alkyl group, a straight or branched alkyl group of H' or Cl_6. X is F, C1, Br, ί, RS〇3, RC〇2, BF4, PF6 or n(s〇3CF3)2 , ', each R is independently a phenyl group of Ci·5 or an alkyl group of Cl·5. Therefore, x is a relative anion of n-imidazole ion. Y is -COOH, which is used as a functional group for copolymerization. The positive ion of the imidazolium salt compound (formula (I)) used in the present invention is one having two carboxyl groups on the imidazolium molecular group, that is, having two carboxyl groups. Imidazole derivative. (b) 99.9 mol% to 50 mol%, preferably 98 mol% to 85 mol% and more preferably 95 mol% to 93 mol% of choice from r6-〇2C_r5_c〇2r6 , H2NR C02R, h2N-R9-NH2, and combinations thereof a comonomer of the group: wherein R is phenyl, n-yl, biphenyl, or _(CH2)b_ and its isomers, b is from 1 to 20, more than an integer of from 8 to R. a group, a naphthyl group, a biphenyl group, or a - (CH2V and its isomers, c is ! to 2 〇, preferably an integer from i to 1 。. r6 is hydrogen or c" alkyl, preferably hydrogen Or & calcined. r8 is chlorine or c) ^, and preferably hydrogen, or Ci4 silk. rU_ (ch or its isomer, t is 1 to 40, preferably) to 12 In the above-mentioned (4) and (8) comonomers, the ratio of the carboxyl group to the amine group is preferably such that the polymerization reaction of the comonomer can be carried out in a solvent-free state at a temperature of from 16 〇 to 26 (TC ' The reaction time is 6_2 hrs. In addition, the polymerization reaction can also be carried out in a solvent state, wherein the above solvent ketone (NMP), dimethylformamide (dm T violent alkane '- (, ) Methylacetamide (DMAc) and ion > trough solution (1.*Oil_etc., the polymerization temperature is between 6. 2 and 2, and the reaction time is 1,295,574 for 6-30 hours. The above ionic solution can be I Right J Dan has the following chemical formulas 2 and b are independent of C" Alkyl. The imidazole-containing organism of the present invention is modified to form a salt which is formed in the imide and is converted into a carboxylic acid substituent, that is, an ugly mono-, and a T-electrode has two at the end. Monomer \ (a) ° The comonomer (4) and the monomer of the nylon (co-polymerization of the cations, the positive salt of the light salt, the carboxyl group is involved in the polymerization reaction and is located in the formed J On the main chain of the character, you can lick too much nR A, ~ the ash hoof of the wind ash mouth... The copolymer of the imidazolium salt. The fabric or film obtained by the compound of the present invention may have characteristics of antistatic property, hydrophilicity, and southern dyeing fastness. The above and other objects, features and advantages of the present invention will become more <RTIgt; 2. Synthesis of Compound Compound 2 and Compound 2b) Synthesis of Compound 2 First, the present invention can be carried out by using an odor-containing salic monomer reaction (Compound 1) having a dimercapto group under the acetone solvent and an anion of acetone. When exchanged, a second slow-based taste with PF6 as an anion can be obtained. Sit on salt compounds (see the procedure below). 1295674 H〇〇C^i0N^ Compound 1
COOH KPF^ 丙 w HOOC^^-v,COOH KPF^ 丙 w HOOC^^-v,
COOH 化合物2 將55公克（0·30 mol)之六氟磷酸鉀（KPF6)加入含有50公克 (0.23 mol)化合物1之500毫升的丙酮溶液中，並於室溫不擾掉 五天。將反應溶液過濾，且濃縮濾液後，即可得油狀產物之化 合物2。 化合物2之光譜資料1H NMR(d6-DMSO, 20〇MHz): δ 8·85(1Η)，7·56(2Η)，4·39(4Η)，3·67(4Η)，2·16(4Η)。 化合物2a之合成： 與化合物2之合成方法相同’但其中係以四氟删酸舒 KBF4(37.8 g，0.30 mol)替代六氟填酸鉀（KPF6)。COOH Compound 2 55 g (0·30 mol) of potassium hexafluorophosphate (KPF6) was added to a solution of 50 g (0.23 mol) of Compound 1 in 500 ml of acetone, and was not disturbed for five days at room temperature. After the reaction solution was filtered, and the filtrate was concentrated, Compound 2 was obtained as an oil. Spectroscopic data of Compound 2 1H NMR (d6-DMSO, 20 〇MHz): δ 8·85 (1Η), 7.56 (2Η), 4·39 (4Η), 3.67 (4Η), 2·16 ( 4Η). Synthesis of Compound 2a: The same procedure as for the synthesis of Compound 2 'But the hexafluoro-sodium sulphate (KPF6) was replaced by THF (37.8 g, 0.30 mol).
H〇〇C-^^C^C〇〇H^ HOOC^^^COOH 化合物1 化合物2a 化合物2b之合成： 與化合物2之合成方法相同，但是以雙三氟磺胺 KN(S02CF3)2 (95.7 g，0.30 mol)替代六 I填®复鉀（KPF6)。 〜 KN(S02CF3)2 n(so2cf3)2- HOOC0◎〜C00H H00C/^〜纖 化合物1 化合物2a 實施例1 :含六氟磷酸鹽咪唑單體（化合物2)之尼龍66共聚合物 (化合物5)之製造 利用上述合成例1所獲得之具有二羧基的六氟碟酸味唑單 體（化合物2)進行本發明之含咪唑鹽尼龍66共聚合物之製造。 尼龍66乃由1，6—己二胺及1，6—己二酸脫水聚合而得，由 1295674 於所用的胺及酸各含有六個碳原子，因而將此種聚合物特稱為 尼龍66。形成本發明含味唾鹽之尼龍66共聚合物之反應式如 下： _ pp 0 HOOC0i0i^-COOH + + 0 化合物2 化合物3 化合物4 Η Ο 化合物5 取33克（0.1 mol)合成例1所獲得之具有二羧基的六氟磷酸 鹽咪唑單體（化合物2)與78克（0.4 mol)量之己二酸二酯單體（化 合物3)，以及58克（0.5 mol)量之己二胺單體（化合物4)混合均 勻後，於110°C下攪拌30分鐘，接著加入0.3克（1000 ppm)量之 三丁基錫（TBT)後，逐漸升溫至270°C攪拌3小時，靜置冷卻。 加入100克量之乙酸乙酯進行清洗，接著以100克量之水離心， 取水可溶層加入500克量之曱醇中進行沉降，可獲得白色固體 產物（化合物5)，即本發明之含咪唑鹽之共聚合物。 在反應完成經純化後，由1H NMR可確定聚合反應之進 行，此聚合物產物之分解溫度（Td)為337.0°C，而當加熱至450 °C時，其裂解17.1%，熔點溫度（Tm)為257°C，冷卻結晶溫度（Tcc) 為178.2°C。利用以聚苯乙烯（polystyrene)為標準溶液之膠體穿 透層析法（gel permeation chromatography ; GPC)測量聚合物產物 (化合物5)之重量平均分子量（MW)為25,000。此聚合物產物中， 其咪唑單體··己二酸二酯單體之理論值為1.0: 4.0,而經由NMR 光譜計算所得之咪唑單體：己二酸二酯單體為1·00 : 3.95。 化合物5之光譜資料1H NMR(CF3COOD，200MHz): δ 9·08, 7·78, 4·63, 4.45, 4.17, 2.69, 2.20, 1.85 ° 1295674 FT-IR : 3436, 1715, 1463, 1203, 1 127, 1028 cnT1。 實施例2 :含四氟硼酸鹽咪唑單體（化合物2a)之尼龍66共聚合 物（化合物5a)之製造 與實施例1之合成方法相同，但是以四氟硼酸鹽咪唑單體 (化合物2a) 27.3克（0·1 mol)替代六氟磷酸鹽咪唑單體（化合物 2)，得到尼龍66共聚合物（化合物5a)，其分解溫度（Td)為330 °C，而當加熱至450°C時則裂解22%，熔點溫度（Tm)為251°C。 HOOC0]0^COOH +、又八八f + Η2Ν^/^νη2 ο 化合物2a 化合物3 化合物4 Η Ο 化合物5a 實施例3 :含六氟磷酸鹽咪唑單體（化合物2)之尼龍6共聚合物 (化合物7)之製造· 利用上述合成例1所獲得之具有二羧基的六氟磷酸咪唑單 體（化合物2)進行本發明之含咪唑鹽尼龍6共聚合物之製造。尼 龍6乃由六個碳數之己内醯胺（Caprolactam)經開環所聚合而成 之聚合物，因而將此種聚合物特稱為尼龍6。形成本發明含咪唑 鹽之尼龍6共聚合物之反應式如下： 12 1295674 HOOC、 化合物2 ^COOH + Caprolactam + H2N ~(hn 人’H〇〇C-^^C^C〇〇H^ HOOC^^^COOH Compound 1 Compound 2a Synthesis of Compound 2b: Same as Compound 2, but with bistrifluorosulfonamide KN(S02CF3)2 (95.7 g , 0.30 mol) instead of six I filled ® potassium (KPF6). ~ KN(S02CF3)2 n(so2cf3)2- HOOC0◎~C00H H00C/^~Fiber Compound 1 Compound 2a Example 1: Nylon 66 Copolymer Containing Hexafluorophosphate Imidazole Monomer (Compound 2) (Compound 5 The production of the imidazolium salt-containing nylon 66 copolymer of the present invention was carried out by using the dihydroxy-containing hexafluorodisazozolium monomer (Compound 2) obtained in the above Synthesis Example 1. Nylon 66 is obtained by dehydration polymerization of 1,6-hexanediamine and 1,6-hexanedicarboxylic acid. The amine and acid used in 1295756 have six carbon atoms, so the polymer is called nylon 66. . The reaction formula for forming the nylon 66 copolymer of the taste-containing saliva salt of the present invention is as follows: _ pp 0 HOOC0i0i^-COOH + + 0 compound 2 compound 3 compound 4 Η 化合物 compound 5 is obtained by taking 33 g (0.1 mol) of Synthesis Example 1. a hexafluorophosphate imidazole monomer having a dicarboxyl group (Compound 2) and 78 g (0.4 mol) of an adipate diester monomer (Compound 3), and 58 g (0.5 mol) of hexamethylenediamine alone After the mixture (Compound 4) was uniformly mixed, the mixture was stirred at 110 ° C for 30 minutes, and then 0.3 g (1000 ppm) of tributyltin (TBT) was added thereto, and the mixture was gradually heated to 270 ° C for 3 hours, and allowed to stand for cooling. Add 100 g of ethyl acetate for washing, then centrifuge with 100 g of water, and add a water-soluble layer to 500 g of sterol to precipitate, to obtain a white solid product (compound 5), which is included in the present invention. a copolymer of an imidazolium salt. After the completion of the reaction, the polymerization was confirmed by 1H NMR. The decomposition temperature (Td) of the polymer product was 337.0 ° C, and when heated to 450 ° C, it was cleaved by 17.1%, and the melting point temperature (Tm). The temperature was 257 ° C and the cooling crystallization temperature (Tcc) was 178.2 ° C. The weight average molecular weight (MW) of the polymer product (Compound 5) was measured by gel permeation chromatography (GPC) using polystyrene as a standard solution to 25,000. The theoretical value of the imidazole monomer·adipate diester monomer in the polymer product is 1.0:4.0, and the imidazole monomer:dipic acid diester monomer calculated by NMR spectroscopy is 1·00: 3.95. Spectroscopic data for Compound 5 1H NMR (CF3COOD, 200MHz): δ 9·08, 7·78, 4·63, 4.45, 4.17, 2.69, 2.20, 1.85 ° 1295674 FT-IR : 3436, 1715, 1463, 1203, 1 127, 1028 cnT1. Example 2: The nylon 66 copolymer (Compound 5a) containing a tetrafluoroborate imidazole monomer (Compound 2a) was produced in the same manner as in the synthesis method of Example 1, except that the tetrafluoroborate imidazole monomer (Compound 2a) was used. 27.3 g (0.1 mol) in place of the hexafluorophosphate imidazole monomer (compound 2) to give a nylon 66 copolymer (compound 5a) having a decomposition temperature (Td) of 330 ° C and heating to 450 ° C At the time, the crack was 22%, and the melting point temperature (Tm) was 251 °C. HOOC0]0^COOH +, yet eighty-eight f + Η2Ν^/^νη2 ο Compound 2a Compound 3 Compound 4 Η 化合物 Compound 5a Example 3: Nylon 6 copolymer containing hexafluorophosphate imidazole monomer (Compound 2) (Product 7) Production The imidazole salt-containing nylon 6 copolymer of the present invention was produced by using the dicarboxyl group of hexafluoroimidazole monomer (compound 2) obtained in the above Synthesis Example 1. Nilong 6 is a polymer obtained by polymerizing six carbon numbers of caprolactam by ring opening, and thus this polymer is specifically referred to as nylon 6. The reaction formula for forming the imidazole salt-containing nylon 6 copolymer of the present invention is as follows: 12 1295674 HOOC, compound 2 ^COOH + Caprolactam + H2N ~ (hn person'
化合物7 取33克（0·1 mol)量合成例1所獲得之具有二羧基的六氟磷 酸味嗤單體（化合物2)與113克（1.0 mol)量之己内醯胺（化合物 6)，以及11.6克（0·1 mol)量之己二胺單體（化合物4)混合均勻 後，於110°C下攪拌30分鐘，接著加入0.3克（1000 ppm)量之三 丁基錫（TBT)後，逐漸升溫至250t攪拌3小時，靜置冷卻。加 入100克量之乙酸乙酯進行清洗，接著以1〇〇克量之水離心， 取水可溶層加入500克量之曱醇中進行沉降，可獲得白色固體 產物（化合物7)，亦即本發明之含咪唑鹽之共聚合物。 在反應完成經純化後，由1H NMR可確定聚合反應之進 行，此聚合物產物之分解溫度（Td)為310.0°C，而當加熱至450 °C時，其裂解27.0%，熔點溫度（Tm)為201°C，冷卻結晶溫度（Tcc) 為164,2°c。利用以聚苯乙稀（polyStyrene)為標準溶液之膠體穿 透層析法（gel permeation chromatography ; GPC)測量聚合物產物 (化合物7)之重量平均分子量（MW)為23,000。此聚合物產物中 咪唑單體··己二酸二酯單體之理論值為1.0 : 1〇·〇，而經由NMR 光譜計算所得之咪唑單體：己二酸二酯單體為1.0 : 9.7。 化合物7之光譜資料1H NMR(CF3COOD，200MHz): δ 9.08, 7.8, 4.63, 4·5, 4.13, 2.71，2·20, 1.8卜 FT-IR ·· 3432, 1712, 1463, 1200, 1120, 1022 cnT1。 實施例4 ··含四氟硼酸鹽咪唑單體（化合物2a)之尼龍6共聚合物 (化合物7a)之製造 13 1295674 與實施例3之合成方法相同，但是以四氟硼酸鹽味σ坐單體 (化合物2a) 27·3克（0.1 mol)替代六氟磷酸鹽咪唑單體（化人物 2)，得到尼龍6共聚合物（化合物7a)，其分解溫度（Td)為3〇(Γ(：， 而當加熱至450°C時則裂解30%，熔點溫度（Tm)為i97t。 NH2 化合物2a Ο 化合物6 Ο 化合物4 ΟCompound 7 was obtained in an amount of 33 g (0.1 mol) of a hexafluorophosphate miso monomer (Compound 2) having a dicarboxy group obtained in Synthesis Example 1 and 113 g (1.0 mol) of caprolactam (Compound 6). And 11.6 g (0.1 mol) of the hexamethylenediamine monomer (Compound 4) was uniformly mixed, and then stirred at 110 ° C for 30 minutes, followed by adding 0.3 g (1000 ppm) of tributyltin (TBT). The temperature was gradually raised to 250 t and stirred for 3 hours, and allowed to stand for cooling. Add 100 g of ethyl acetate for washing, then centrifuge with 1 gram of water, and take a water-soluble layer and add 500 g of sterol to precipitate to obtain a white solid product (Compound 7), which is The imidazole salt-containing copolymer of the invention. After the completion of the reaction, the polymerization was confirmed by 1H NMR. The decomposition temperature (Td) of the polymer product was 310.0 ° C, and when heated to 450 ° C, the cracking was 27.0%, and the melting point temperature (Tm) ) is 201 ° C, and the cooling crystallization temperature (Tcc) is 164, 2 ° c. The weight average molecular weight (MW) of the polymer product (Compound 7) was measured by gel permeation chromatography (GPC) using polystyrene as a standard solution to 23,000. The theoretical value of the imidazole monomer·adipate diester monomer in the polymer product is 1.0:1〇·〇, and the imidazole monomer obtained by NMR spectroscopy: adipic acid diester monomer is 1.0: 9.7 . Spectroscopic data of Compound 7 1H NMR (CF3COOD, 200 MHz): δ 9.08, 7.8, 4.63, 4·5, 4.13, 2.71, 2·20, 1.8 FT-IR ····················· cnT1. Example 4 · Preparation of Nylon 6 Copolymer (Compound 7a) Containing Tetrafluoroborate Imidazole Monomer (Compound 2a) 13 1295674 Same as the synthesis method of Example 3, but with tetrafluoroborate taste σ (Compound 2a) 27·3 g (0.1 mol) instead of hexafluorophosphate imidazole monomer (Human 2), a nylon 6 copolymer (compound 7a) having a decomposition temperature (Td) of 3 〇 (Γ(Γ) :, and when heated to 450 ° C, it is cracked by 30%, and the melting point temperature (Tm) is i97t. NH2 compound 2a Ο compound 6 Ο compound 4 Ο
化合物7a 實施例5 :含雙三氟磺胺鹽N(S〇2CF3)2單體（化合物2b)之尼龍 6共聚合物（化合物7b)之製造 與實施例3之合成方法相同，但是以含雙三氟續胺鹽 N(S02CF3)2單體（化合物2b) 46.6 g(0.1 mol)替代六氟磷酸鹽咪 唑單體（化合物2)，得到尼龍6共聚合物（化合物7b)，其分解溫 度（Td)為315°C，而當加熱至450°C時則裂解14%，熔點溫度（Tm) 為 199〇C。 NH9Compound 7a Example 5: The nylon 6 copolymer (Compound 7b) containing the bistrifluorosulfonamide N(S〇2CF3)2 monomer (Compound 2b) was produced in the same manner as in Example 3 except that it contained Trifluoro-reacting amine salt N(S02CF3)2 monomer (compound 2b) 46.6 g (0.1 mol) instead of hexafluorophosphate imidazole monomer (compound 2), to obtain nylon 6 copolymer (compound 7b), its decomposition temperature ( Td) is 315 ° C, and when heated to 450 ° C, it is cracked by 14% and the melting point temperature (Tm) is 199 ° C. NH9
N(S02CF3)2- HOOC^.Jp^x^COOHN(S02CF3)2- HOOC^.Jp^x^COOH
Caprolactam + H2N 化合物2b 化合物6 化合物4 O N(S02CF3)2- ο ο 化合物7 b 化合物7b之光譜資料1H NMR(CF3COOD，200MHz): δ 9,0, 8·1，4·7, 4·4, 4·2, 2.3, 2.2, 1·9。 FT-IR : 3442, 1718, 1467, 1200, 1 125, 1020 cm·1。 14 1295674 實施例6··含咪唑鹽之尼龍6共聚合物於離子溶液中之製造 本發明含有咪嗤鹽之尼龍共聚合物係可於例如NMP、 DMF'DMAc以及離子溶液等溶劑中製造，本實施例乃於下式 之離子溶液中進行本發明含咪唑鹽之尼龍6共聚合物之製造， 其中Rn為甲基，Ri2為丁基，X為PF6。Caprolactam + H2N Compound 2b Compound 6 Compound 4 ON(S02CF3)2- ο ο Compound 7 b Spectrum of Compound 7b 1H NMR (CF3COOD, 200MHz): δ 9,0, 8·1,4·7, 4·4, 4·2, 2.3, 2.2, 1·9. FT-IR: 3442, 1718, 1467, 1200, 1 125, 1020 cm·1. 14 1295674 Example 6 · Preparation of imidazole salt-containing nylon 6 copolymer in ionic solution The nylon copolymer of the present invention containing a sulfonium salt can be produced, for example, in a solvent such as NMP, DMF 'DMAc, and an ionic solution. In the present embodiment, the imidazole salt-containing nylon 6 copolymer was produced in the ionic solution of the following formula, wherein Rn is a methyl group, Ri2 is a butyl group, and X is PF6.
取33克（〇·ΐ m〇l)量合成例1所獲得之具有二羧基的六氟磷 酉文咪唑單體（化合物2)與113克（1.0 mol)量之己内醯胺（化合物 6)，以及11·6克（0.1 m〇l)量之己二胺單體（化合物4)加入上式之 離子溶液30克中混合均勻，於U(rc下攪拌3〇分鐘，接著加入 0.3克（10〇〇ppm)量之三丁基錫（TBT)後，逐漸升溫至16〇t：攪拌 26小時，靜置冷卻。加入1〇〇克量之乙酸乙酯進行清洗，接著 以100克量之水離心，取水可溶層加入5〇〇克量之甲醇中進行 /儿降，可獲得白色固體產物（化合物7)，亦即本發明於離子溶液 中所製造之含咪唑鹽之共聚合物。 在反應完成經純化後，由】H NMR可確定聚合反應之進 订，此聚合物產物之分解溫度（Td)為33〇.〇t：，而當加熱至45〇 、時，其裂解16·0%，熔融溫度（丁叫為2〇5t：，冷卻結晶溫度（Tcc) 為169 c。利用以聚苯乙烯（p0]ystyrene)為標準溶液之膠體穿透 層析法（gel permeation chromatography; GPC)測量聚合物產物 1化合物7)之重量平均分子量（MW)為28,000。此聚合物產物中 米唾單體·己二酸二醋單體之理論值為1〇 : 1G()，而經由丽r 光谱計算所得之味嗤單體··己二酸二_單體為丨力·· 9·7。 15 1295674 於離子溶液之溶液中所合成化合物7之光譜資料]h NMR(D20, 200MHz): ' δ 9·08, 7·8, 4.63, 4.5, 4.13, 2.71，2.20, 1.81。 FT-IR : 3432, 1712, 1463, 1200, 1120, 1022 cm·1。 聚合物之回潮率、抗靜電性以及染色性之測試結果·· 對本發明實施例1-5之聚醯胺共聚合物薄膜進行回潮率、 抗靜電性以及染色性之試驗。 測試例1(抗靜電試驗）： 將實施例2及實施例4之含四氟硼酸鹽咪唑單體之尼龍66 及尼龍6共聚合物（化合物化及化合物7a)分別製成薄膜，面積 為20mm x40mm，放置於1〇0。(：烘箱中烘乾1〇小時。電阻值 測試儀器為低電壓四點式電阻值測試儀，固定電流〇〇〇1安培 (Is)，量測其電壓（Vm)，每一試片量測片電阻2〇次，最後以5；=：(πΐ /1112)(¥“18)換算電阻。化合物元以及化合物以乃分別測得電 阻值為2xl〇8歐姆公分以及3χ1〇7歐姆公分；而以尼龍66及 尼龍6作為對照之實驗所測得之電阻值則分別為7χΐ〇9歐姆公 分以及5xl〇8歐姆公分。 測試例2(回潮率試驗）： 將實施例2及實施例4令含四氟硼酸鹽咪唑單體之尼龍66 及尼龍6共聚合物（化合物5&及化合物7a)分別製成薄膜，面積 為20mm X40mm，放置於100。€烘箱中烘乾1〇小時。然後置 於23°C’65RH%之條件下，於24小時後所測量其增加之重量（吸 水）乃分別為4.9%及5.3%，而以尼龍66及尼龍6作為對照^驗 之吸水值則分別為4.0%及4.2%。 、， 16 1295674 測試例3 (染色試驗）： 將實施例I-5之共聚合物分別依照測試例1之方式製成薄 膜，於約98°C之水溶液中，加入陰離子染料’進行染色試驗， 約30分鐘後，皂洗。當水洗50次後，其水洗堅牢度大於4級， 而以尼龍66及尼龍6為對照之實驗，當水洗20次後，其水洗 堅牢度則小於4級。 雖然本發明已以較佳實施例揭露如上，然其並非用以限定 =發明。任何熟習此技藝者，在不脫離本發明之精神和範圍内， =作些許之更動與潤飾。因此本發明之保護範圍當視後附之 申凊專利範圍所界定者為準。 、 17 1295674 【圖式簡單說明】 無。 【主要元件符號說明】 無0Taking 33 g (〇·ΐ m〇l) of the hexafluorophosphonium imidazole monomer (Compound 2) having a dicarboxyl group obtained in Synthesis Example 1 and 113 g (1.0 mol) of caprolactam (Compound 6) And 11,6 g (0.1 m〇l) of hexamethylenediamine monomer (Compound 4) was added to 30 g of the above ionic solution and mixed uniformly, stirred at U (rc for 3 〇 minutes, then added 0.3 g) After (10 〇〇ppm) amount of tributyltin (TBT), gradually increase the temperature to 16 〇t: stir for 26 hours, let stand for cooling. Add 1 gram of ethyl acetate for washing, then 100 gram of water After centrifugation, the water-soluble layer was added to methanol in an amount of 5 gram, and a white solid product (compound 7), that is, the imidazolium-containing copolymer produced in the ionic solution of the present invention was obtained. After the completion of the reaction, the polymerization was determined by H NMR. The decomposition temperature (Td) of the polymer product was 33 〇.〇t:, and when heated to 45 〇, it was cleaved 16·0. %, melting temperature (4:5t:, cooling crystallization temperature (Tcc) is 169 c. It is dissolved in polystyrene (p0)ystyrene) The gel permeation chromatography (GPC) measures the weight average molecular weight (MW) of the polymer product 1 compound 7) to 28,000. The polymer product is the rice succinimide/adipic acid diacetate monomer. The theoretical value is 1〇: 1G(), and the miso monomer······························································ Spectroscopic data of Compound 7]h NMR (D20, 200 MHz): ' δ 9·08, 7·8, 4.63, 4.5, 4.13, 2.71, 2.20, 1.81. FT-IR : 3432, 1712, 1463, 1200, 1120, 1022 cm·1. Test results of moisture regain, antistatic property and dyeability of the polymer·· The test of moisture regain, antistatic property and dyeability of the polyamidamide copolymer film of Examples 1 to 5 of the present invention. Test Example 1 (antistatic test): The nylon 66 and nylon 6 copolymers (compounding compound and compound 7a) of the tetrafluoroborate imidazole monomer of Example 2 and Example 4 were respectively formed into a film having an area of 20 mm. X40mm, placed at 1〇0. (: drying in an oven for 1 hour. The resistance value test instrument is low voltage four-point electric Value tester, fixed current 〇〇〇1 amp (Is), measure its voltage (Vm), measure the resistance of each test piece 2 times, and finally 5;=:(πΐ /1112)(¥"18 The resistance is calculated. The resistance of the compound and the compound is 2xl〇8 ohm cm and 3χ1〇7 ohm centimeters respectively; and the resistance measured by the experiment using nylon 66 and nylon 6 as the control is 7χΐ〇. 9 ohm centimeters and 5xl 〇 8 ohm centimeters. Test Example 2 (moisture regain test): In Example 2 and Example 4, nylon 66 and nylon 6 copolymers (compound 5 & and compound 7a) containing tetrafluoroborate imidazole monomer were respectively formed into a film having an area of 20mm X40mm, placed at 100. Dry in an oven for 1 hour. Then, under the condition of 23 ° C '65 RH%, the weight increase (water absorption) measured after 24 hours was 4.9% and 5.3%, respectively, and the water absorption value of nylon 66 and nylon 6 as the control was measured. They were 4.0% and 4.2% respectively. 16 1295674 Test Example 3 (dyeing test): The copolymer of Example I-5 was separately formed into a film in the manner of Test Example 1, and an anionic dye was added to an aqueous solution at about 98 ° C for a dyeing test. After about 30 minutes, soap. After washing 50 times, the washing fastness was greater than 4, while the experiment with nylon 66 and nylon 6 as the control, when washed 20 times, the washing fastness was less than 4 grades. Although the present invention has been disclosed above in the preferred embodiments, it is not intended to be limiting. Anyone skilled in the art can make some changes and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention is defined by the scope of the appended claims. , 17 1295674 [Simple description of the diagram] None. [Main component symbol description] No 0
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW93140981A TWI295674B (en) | 2004-12-28 | 2004-12-28 | Imidazolium-based nylon copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW93140981A TWI295674B (en) | 2004-12-28 | 2004-12-28 | Imidazolium-based nylon copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200621854A TW200621854A (en) | 2006-07-01 |
| TWI295674B true TWI295674B (en) | 2008-04-11 |
Family
ID=45068510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW93140981A TWI295674B (en) | 2004-12-28 | 2004-12-28 | Imidazolium-based nylon copolymer |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI295674B (en) |
-
2004
- 2004-12-28 TW TW93140981A patent/TWI295674B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW200621854A (en) | 2006-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7371128B2 (en) | High molecular weight furan-based aramid and its manufacturing method and use | |
| CN104478838B (en) | Phenylethynyl-containing dianhydride monomer, and synthesis method and application thereof | |
| CN104837809B (en) | Diamines comprising hexafluoroisopropanol base, polyimides and polyamide using it, its cyclisation thing and its manufacture method | |
| Bazzar et al. | Novel fluorescent light-emitting polymer composites bearing 1, 2, 4-triazole and quinoxaline moieties: Reinforcement and thermal stabilization with silicon carbide nanoparticles by epoxide functionalization | |
| JPH01188527A (en) | Polymer and its production | |
| Ghaemy et al. | Synthesis and characterization of new imidazole and fluorene–bisphenol based polyamides: Thermal, photophysical and antibacterial properties | |
| JP4137583B2 (en) | Use of sulfonic, phosphonic and phosphoric acids as dopants for polyaniline and conductive polyaniline based composites | |
| Hsiao et al. | Fluorescent and electrochromic aromatic polyamides with 4‐tert‐butyltriphenylamine chromophore | |
| Hsiao et al. | Highly stable electrochromic polyamides based on N, N‐bis (4‐aminophenyl)‐N′, N′‐bis (4‐tert‐butylphenyl)‐1, 4‐phenylenediamine | |
| JPH04501881A (en) | Synthetic polyamides and their salts | |
| Yen et al. | Synthesis and unexpected electrochemical behavior of the triphenylamine‐based aramids with ortho‐and para‐trimethyl‐protective substituents | |
| US7838091B2 (en) | Aromatic polyamide, polymerization method thereof, and optical film using the same | |
| JP3631910B2 (en) | Method for producing highly conductive aniline polymer | |
| TWI295674B (en) | Imidazolium-based nylon copolymer | |
| TW200909427A (en) | Triphenylamine-containing bismaleimide compound and preparation thereof | |
| Nakabayashi et al. | Rylene bisimide-based nanoparticles with cross-linked core and thermoresponsive shell using poly (vinyl amine)-based block copolymers | |
| Liou et al. | Synthesis, photoluminescence, and electrochromic properties of wholly aromatic polyamides bearing naphthylamine chromophores | |
| Shao et al. | An unexpected discovery of a one-pot synthesis for carbazole-based diamine and the electrochromic properties of the derived polymers | |
| US2989495A (en) | Solution of wholly aromatic polyamides in liquid organic amine solvents | |
| CN100467514C (en) | Nylon copolymer containing imidazole salt | |
| CN113698306A (en) | Diamine compound containing symmetrical double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof | |
| US3676525A (en) | High molecular weight aromatic polyamides having an affinity for basic dyes | |
| JPH05255504A (en) | Polyamide-imide containing ionic group | |
| Voss et al. | Polymeric colorants: Statistical copolymers of indigo building blocks with defined structures | |
| US8088932B2 (en) | Pentaaryldiamine-containing bismaleimide compound and method of producing the compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |