WO2004013218A1 - Antistatic agents and polymer compositions derived therefrom - Google Patents
Antistatic agents and polymer compositions derived therefrom Download PDFInfo
- Publication number
- WO2004013218A1 WO2004013218A1 PCT/US2003/019602 US0319602W WO2004013218A1 WO 2004013218 A1 WO2004013218 A1 WO 2004013218A1 US 0319602 W US0319602 W US 0319602W WO 2004013218 A1 WO2004013218 A1 WO 2004013218A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- unsubstituted
- substituted
- aliphatic
- functional group
- aromatic
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 81
- 229920000642 polymer Polymers 0.000 title claims description 44
- 239000002216 antistatic agent Substances 0.000 title description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 62
- 125000003118 aryl group Chemical group 0.000 claims abstract description 57
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 47
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 polyestercarbonate Polymers 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 27
- 230000002378 acidificating effect Effects 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 15
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003456 ion exchange resin Substances 0.000 claims description 8
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000004417 polycarbonate Substances 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- HWEXKRHYVOGVDA-UHFFFAOYSA-M sodium;3-trimethylsilylpropane-1-sulfonate Chemical compound [Na+].C[Si](C)(C)CCCS([O-])(=O)=O HWEXKRHYVOGVDA-UHFFFAOYSA-M 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 125000004122 cyclic group Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229920005992 thermoplastic resin Polymers 0.000 claims description 3
- 238000012695 Interfacial polymerization Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 230000000712 assembly Effects 0.000 claims description 2
- 238000000429 assembly Methods 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920001470 polyketone Polymers 0.000 claims description 2
- 229920002959 polymer blend Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- ZOMVKCHODRHQEV-UHFFFAOYSA-M tetraethylphosphanium;hydroxide Chemical compound [OH-].CC[P+](CC)(CC)CC ZOMVKCHODRHQEV-UHFFFAOYSA-M 0.000 claims description 2
- XVHQFGPOVXTXPD-UHFFFAOYSA-M tetraphenylphosphanium;hydroxide Chemical compound [OH-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XVHQFGPOVXTXPD-UHFFFAOYSA-M 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 11
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 230000003068 static effect Effects 0.000 description 11
- 238000000465 moulding Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
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- 229920003002 synthetic resin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
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- 125000004799 bromophenyl group Chemical group 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 125000004802 cyanophenyl group Chemical group 0.000 description 2
- 125000004188 dichlorophenyl group Chemical group 0.000 description 2
- 125000004212 difluorophenyl group Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 125000005059 halophenyl group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 230000001617 migratory effect Effects 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 125000006501 nitrophenyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
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- 238000005507 spraying Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical class C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- NJMIRMHNYQIHST-UHFFFAOYSA-M 2-dodecylbenzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O NJMIRMHNYQIHST-UHFFFAOYSA-M 0.000 description 1
- KWXICGTUELOLSQ-UHFFFAOYSA-M 4-dodecylbenzenesulfonate Chemical compound CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 KWXICGTUELOLSQ-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- VHTDHSVPBYDDAM-UHFFFAOYSA-N benzyl(triethyl)phosphanium Chemical compound CC[P+](CC)(CC)CC1=CC=CC=C1 VHTDHSVPBYDDAM-UHFFFAOYSA-N 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- XNTQTOLGQFJZMO-UHFFFAOYSA-N benzyl(trimethyl)phosphanium Chemical compound C[P+](C)(C)CC1=CC=CC=C1 XNTQTOLGQFJZMO-UHFFFAOYSA-N 0.000 description 1
- QUCVNPJIPOQRLJ-UHFFFAOYSA-N benzyl(triphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 QUCVNPJIPOQRLJ-UHFFFAOYSA-N 0.000 description 1
- BNQRPLGZFADFGA-UHFFFAOYSA-N benzyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 BNQRPLGZFADFGA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
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- TXPMUPUOSOZCCS-UHFFFAOYSA-N hexadecyl(trimethyl)phosphanium Chemical compound CCCCCCCCCCCCCCCC[P+](C)(C)C TXPMUPUOSOZCCS-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
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- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- AHCKRTXGDNIJSK-UHFFFAOYSA-N methyl(trioctyl)phosphanium Chemical compound CCCCCCCC[P+](C)(CCCCCCCC)CCCCCCCC AHCKRTXGDNIJSK-UHFFFAOYSA-N 0.000 description 1
- PHUUEJUSWPFFOG-UHFFFAOYSA-N methyl(triphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 PHUUEJUSWPFFOG-UHFFFAOYSA-N 0.000 description 1
- AZFQCTBZOPUVOW-UHFFFAOYSA-N methyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 AZFQCTBZOPUVOW-UHFFFAOYSA-N 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
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- 125000000962 organic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 description 1
- CHYBTAZWINMGHA-UHFFFAOYSA-N tetraoctylazanium Chemical compound CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC CHYBTAZWINMGHA-UHFFFAOYSA-N 0.000 description 1
- CZMILNXHOAKSBR-UHFFFAOYSA-N tetraphenylazanium Chemical compound C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CZMILNXHOAKSBR-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- GFVKHYGXCQWRON-UHFFFAOYSA-N tributyl(ethyl)azanium Chemical compound CCCC[N+](CC)(CCCC)CCCC GFVKHYGXCQWRON-UHFFFAOYSA-N 0.000 description 1
- HOMONHWYLOPSLL-UHFFFAOYSA-N tributyl(ethyl)phosphanium Chemical compound CCCC[P+](CC)(CCCC)CCCC HOMONHWYLOPSLL-UHFFFAOYSA-N 0.000 description 1
- HNTQYVHJXDXWDT-UHFFFAOYSA-N tributyl(hexadecyl)azanium Chemical compound CCCCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC HNTQYVHJXDXWDT-UHFFFAOYSA-N 0.000 description 1
- OKBQUWUVZGPEQZ-UHFFFAOYSA-N tributyl(hexadecyl)phosphanium Chemical compound CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC OKBQUWUVZGPEQZ-UHFFFAOYSA-N 0.000 description 1
- GYOFRJOMHLYJNZ-UHFFFAOYSA-N tributyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC GYOFRJOMHLYJNZ-UHFFFAOYSA-N 0.000 description 1
- YCBRTSYWJMECAH-UHFFFAOYSA-N tributyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC YCBRTSYWJMECAH-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- IKANSXQHJXBNIN-UHFFFAOYSA-N trimethyl(octadecyl)phosphanium Chemical compound CCCCCCCCCCCCCCCCCC[P+](C)(C)C IKANSXQHJXBNIN-UHFFFAOYSA-N 0.000 description 1
- NACZPBOVCXPUJN-UHFFFAOYSA-N tris-decyl(methyl)azanium Chemical compound CCCCCCCCCC[N+](C)(CCCCCCCCCC)CCCCCCCCCC NACZPBOVCXPUJN-UHFFFAOYSA-N 0.000 description 1
- YDEGKXHZLSSIGB-UHFFFAOYSA-N tris-decyl(methyl)phosphanium Chemical compound CCCCCCCCCC[P+](C)(CCCCCCCCCC)CCCCCCCCCC YDEGKXHZLSSIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0075—Antistatics
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
Definitions
- This disclosure relates to new antistatic additives, polymer compositions comprising these additives, as well as methods of making these additives and polymer compositions.
- Antistatic agents constitute a unique class of polymer additives. They prevent an accumulation of static electricity on the surface of an article fabricated of the polymer. They also offer aesthetic values by preventing the accumulation of surface dust on the article.
- lenses of automotive headlamps are typically made of polymers, such as polycarbonates, which have a desirable combination of heat stability, dimensional stability, transparency, and ductility.
- the optics system also sometimes called "Fresnel" necessary to properly focus the headlight beam on the road did not have a smooth profile. Consequently, the dust that accumulated on the lens surface, either during fabrication, or during the service life of the headlamp, was not conspicuously visible. But as the automotive industry moves towards lenses with a smoother profile, the accumulated dust becomes more easily visible, therefore leading to aesthetics issues.
- Conveyor belts are typically made mostly of synthetic polymeric materials.
- Use of plastic in conveyor belts has led to several distinct advantages in conveyor belt technology, such as cleanliness, reliability, decreased noise, low cost to lifetime ratio, modularity, and flexibility.
- plastics-based conveyor systems are being used in hyper clean (class 100 or higher) environments essential for the manufacture of advanced electronics products and systems.
- electrostatic discharge a phenomenon inherent of plastic materials, poses increasing problems to the high technology manufacturers that use plastic conveyor components.
- the buildup of surface charge results in secondary dirt contamination, which has undesirable consequences, especially for precision, high technology electronic components.
- Antistatic agents may be applied in two ways: externally and internally.
- External antistatic agents are applied by spraying the surface, or dipping the polymeric material in a medium containing the antistatic agent. Internal antistatic agents are added to the polymer before processing. For this reason, internal antistatic agents have to be thermally stable and preferably migrate to the surface during processing. Additionally, the incorporation of the antistatic agent should not diminish desirable characteristics of the polymeric material such a transparency and glass transition temperature (Tg).
- Tg transparency and glass transition temperature
- An antistatic additive comprises a quaternary onium organosilicon compound having the formula (I)
- each R 1 independently comprises an aliphatic or aromatic functional groups that may be substituted or unsubstituted
- X comprises phosphorus or nitrogen
- each R independently comprises an aliphatic or aromatic functional group that may be substituted or unsubstituted
- each R 3 independently comprises a hydrogen or an aliphatic or aromatic functional group that may be substituted or unsubstituted
- "n" has a value of about 1 to about 20.
- an antistatic polymer composition comprises a polymer and a quaternary onium organosilicon compound having the formula (I)
- R , X, R , R , and "n" are as previously defined.
- Still another embodiment is a method of making an antistatic quaternary onium organosilicon compound comprising contacting a solution comprising a first solvent and an organosilicon monosulfonic salt having the formula (II)
- each R 2 independently comprises an aliphatic or aromatic functional group that may be substituted or unsubstituted; each R 3 independently comprises a hydrogen or an aliphatic or aromatic functional group that may be substituted or unsubstituted; and "n" has a value of about 1 to about 20 with an acidic medium to generate the corresponding free sulfonic acid; contacting the free sulfonic acid with a quaternary compound to form a mixture, extracting the mixture with a second solvent to provide a solution of a quaternary onium organosilicon compound having the formula (I)
- each R independently comprises an aliphatic or aromatic functional groups that may be substituted or unsubstituted;
- X comprises phosphorus or nitrogen;
- each R independently comprises an aliphatic or aromatic functional group that may be substituted or unsubstituted;
- each R 3 independently comprises an aliphatic or aromatic functional group that may be substituted or unsubstituted; and
- "n" has a value of about 1 to about 20; and evaporating substantially all the solvent from the solution of quaternary onium organosilicon compound.
- a method of making an antistatic thermoplastic polymer composition comprises combining a quaternary onium organosilicon compound with a thermoplastic resin in melt, wherein the organosilicon compound is represented by the formula:
- each R 1 independently comprises a substituted or unsubstituted, aliphatic or aromatic functional group
- X comprises phosphorus or nitrogen
- each R 2 independently comprises a substituted or unsubstituted, aliphatic or aromatic functional group
- each R 3 independently comprises a substituted or unsubstituted, aliphatic functional group, substituted or unsubstituted, aromatic functional group or a hydrogen
- "n" has a value of about 1 to about 20.
- a method of making an antistatic thermoplastic polymer molding composition comprises dry-blending a quaternary onium organosilicon compound with a thermoplastic polymer, wherein the organosilicon compound is represented by the formula:
- each R 1 independently comprises a substituted or unsubstituted, aliphatic or aromatic functional group
- X comprises phosphorus or nitrogen
- each R independently comprises a substituted or unsubstituted, aliphatic or aromatic functional group
- each R 3 independently comprises a substituted or unsubstituted, aliphatic functional group, substituted or unsubstituted, aromatic functional group or a hydrogen
- "n" has a value of about 1 to about 20.
- each R 1 independently comprises aliphatic or aromatic functional groups that may be substituted or unsubstituted;
- X is selected from the group consisting of phosphorus and nitrogen;
- each R 2 independently comprises aliphatic or aromatic functional groups that may be substituted or unsubstituted;
- each R 3 independently comprises a hydrogen or an aliphatic or aromatic functional groups that may be substituted or unsubstituted; and
- "n" has a value of about 1 to about 20 have great utility as antistatic additives in polymeric compositions, particularly thermoplastic polymeric compositions.
- the antistatic additives described herein are thermally stable for the cycle times and temperatures generally employed in polymer processing.
- Polymer compositions comprising the quaternary onium organosilicon compounds maintain their physical properties, such as glass transition temperature, when compared to similar polymer compositions without the quaternary onium organosilicon compounds, even after being formed into the desired shape or article. These advantages make the resulting antistatic polymer compositions valuable in many applications including automotive, electronic, conveyor belt system, and display device applications where effective dissipation of static electricity and/or dust repellency are important requirements. In all embodiments of the disclosure, the term “antistatic” is also meant to imply “antidust”.
- the R 1 groups in the quaternary onium organosilicon compounds depicted hereinabove can assume a wide variation in their structures as long as the structure of the group or groups does not hinder formation of the quaternary onium organosilicon compound.
- Each R 1 group independently comprises a substituted or unsubstituted, aliphatic or aromatic functional group.
- the four R 1 groups bonded to X can all be the same, or they can consist of two, three, or four different functional groups.
- Useful aliphatic R 1 functional groups comprise Cj-C ⁇ 8 linear or branched alkyl, aralkyl, and cycloalkyl groups.
- the aliphatic functional group may further comprise one or more heteroatoms.
- R 1 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-hexadecyl, and n-octadecyl. More preferably, R 1 is n-butyl .
- organic groups containing oxygen atoms include hydrocarbon groups substituted with hydroxyl or alkoxy group. More specifically, the heteroatom containing group includes, but is not limited to hydroxyalkyl groups, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, and hydroxyoctyl; and alkoxyalkyl groups, such as methoxymethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, isopropoxymethyl, n-butoxymethyl, n-butoxyethyl, iso-butoxyethyl, polyalkylene glycol, and the like, including mixtures thereof.
- hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, and hydroxyoctyl
- Useful aromatic R 1 functional groups comprise C 6 -C ⁇ 4 substituted or unsubstituted aromatic groups.
- Unsubstituted aromatic groups may be selected from the group consisting of phenyl, indenyl, biphenyl, 1-naphthyl, 2-naphthyl, anthracenyl, and fluorenyl.
- Substituted aromatic groups may be selected from the group consisting of halophenyl, polyhalophenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, fluorophenyl, difluorophenyl, alkoxyphenyl, alkoxycarbonylphenyl, nitrophenyl, cyanophenyl, alkylphenyl, polyalkylphenyl, tolyl, xylyl, benzyl, isopropylphenyl, isobutylphenyl, ⁇ chloronaphthyl, methylnaphthyl, and isopropylnaphthyl.
- the aromatic functional group may further comprise one or more heteratom containing substituents.
- Examples of the (R' 4 X) + fragment of the quaternary onium organosilicon compound include, but are not limited to, tetramethylammonium, tetramethylphosphonium, tetraethylammonium, tetraethylphosphonium, tetra-n-butylammonium, tetra-n-butylphosphonium, tetra-n-pentylammonium, tetra-n-pentylphosphonium, tetra-n- hexylammonium, tetra-n-hexylphosphonium, tetra-n-heptylammonium, tetra-n- heptylphosphonium, tetra-n-octylammonium, tetra-n-octylphosphonium, tetraphenylammonium, tetraphenylphosphonium, methyltripheny
- Each R 2 group bonded to silicon independently comprises substituted or unsubstituted aliphatic or aromatic, substituted or unsubstituted groups.
- the three R groups bonded to silicon may comprise the same functional group or different functional groups.
- Useful R 2 groups comprise substituted or unsubstituted C]-C] 8 linear and branched alkyl radicals, aralkyl, and cycloalkyl radicals.
- Aliphatic R 2 groups may also comprise one or more heteroatoms.
- R 2 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n- dodecyl, n-hexadecyl, and n-octadecyl. More preferably, R is a methyl radical. R can also be a fluorinated monovalent hydrocarbyl group, such as 3,3,3-trifluoropropyl and other perf oroalkylethyl groups, alpha, alpha, alpha-trifluoromethylphenyl, pentafiuorophenyl, and the like.
- Useful aromatic R 2 functional groups typically comprise substituted or unsubstituted C 6 -C] aromatic groups.
- Exemplary aromatic functional groups include phenyl, indenyl, biphenyl, 1-naphthyl, 2-naphthyl, anthracenyl, and fluorenyl.
- Exemplary substituted aromatic functional groups include halophenyl, polyhalophenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, fluorophenyl, difluorophenyl, alkoxyphenyl, alkoxycarbonylphenyl, nitrophenyl, cyanophenyl, alkylphenyl, polyalkylphenyl, tolyl, xylyl, benzyl, isopropylphenyl, isobutylphenyl, chloronaphthyl, methylnaphthyl, isopropylnaphthyl, and the like.
- the aromatic functional group may also comprise one or more heteroatom containing substituents.
- R 3 groups of the (R 2 C) n fragment of the quaternary onium organosilicon compounds comprise substituted or unsubstituted aliphatic or aromatic functional groups as described above with regard to R 1 and R 2 . Additionally, R 3 may be hydrogen. The R 3 groups may be the same or different. Preferably R 3 is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n- dodecyl, n-hexadecyl, and n-octadecyl. More preferably, R 3 is hydrogen.
- the "n" in the general formula of the quaternary onium organosilicon compounds has a value of about 1 to about 20. In a particular embodiment, "n" has a value of about 3.
- the quaternary onium organosilicon compound has the
- each R is an n-butyl radical
- X is phosphorus or nitrogen
- each R is a methyl radical
- each R" is a hydrogen
- "n” has a value in the range from about 2 to about 10.
- each R 1 is an n-butyl radical
- X is phosphorus or nitrogen
- each R is a methyl radical
- each R " is a hydrogen
- "n” has a value of about 3.
- X is phosphorous.
- the alkali metal "M" in the organosilicon monosulfonic acid salt is selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium. These salts are used as precursors to obtain the corresponding free organosilicon monosulfonic acid.
- the acidic medium that is used to generate the free organosilicon monosulfonic acid comprises strong acids.
- the acidic medium comprises a polymeric, strongly acidic ion exchange resin bearing sulfonic acid groups.
- Suitable examples of polymeric, strongly acidic ion exchange resin bearing sulfonic acid groups include, but are not limited to fluorinated polymeric sulfonic acid resins, such as the Nafion® series of resins (available commercially from Dupont), and sulfonated styrene-divinylbenzene copolymers prepared using from about 0.5 mole percent to about 20 mole percent of divinylbenzene per hundred moles of styrene employed.
- the sulfonated styrene- divinylbenzene copolymers comprise gelular and macroreticular varieties, corresponding to the sulfonated, low and high divinylbenzene-crosslinked styrene copolymers, respectively.
- a gelular resin is Amberlyst-121 (sulfonated, 4% divinylbenzene-crosslinked polystyrene resin) available commercially from Rohm and Haas Company.
- An example of a macroreticular resin is Amberlyst- 15 (sulfonated, 20% divinylbenzene-crosslinked polystyrene resin), also available commercially from Rohm and Haas Company.
- an excess of the acidic medium over the organosilicon monolsulfonic acid salt is employed to ensure essentially complete conversion to the free organosilicon monosulfonic acid.
- Essentially complete conversion is herein defined as greater than about 95%, preferably greater that about 98%, and more preferably greater than about 99%o complete, based on the starting amount of the organosilicon monosulfonic acid salt.
- the acidic medium employed is a sulfonated styrene- divinylbenzene resin, and is used in an amount of about 15 times to about 20 times the number of moles of the alkali metal organosilicon sulfonic acid salt. Higher amounts of the acidic medium can also be employed, but they are generally not required.
- an organosilicon monosulfonic acid salt is contacted with an acidic medium comprising a polymeric acidic resin by introducing a solution comprising the organosilicon monosulfonic acid to the top of a packed bed column containing the acidic resin.
- the alkali metal ions are exchanged for hydrogen ions in the column such that the liquid stream coming out from the bottom of the column contains the corresponding free organosilicon monosulfonic acid.
- contacting is effected by pumping the solution from the bottom of the packed bed column and the solution of the product mixture is collected from the top.
- Suitable solvents for preparing a solution comprising the organosilicon monosulfonic acid salt comprise water, C ⁇ -C 4 aliphatic alcohols, tetrahydrofuran, acetonitrile, C 7 - C 9 aromatic hydrocarbons, and mixtures thereof. Generally the presence of water facilitates the alkali metal ion-hydrogen ion exchange process.
- the free organosilicon monosulfonic acid composition obtained above is neutralized by contacting it with a quaternary compound comprising (XR' 4 ) + Y " , wherein X and R 1 are described above, forming a neutralization mixture.
- Y comprises hydroxide, OCOR 4 , or OR 4 , wherein R 4 comprises a substituted or unsubstituted aliphatic, carbocyclic or aromatic functional group.
- R 4 comprises a substituted or unsubstituted aliphatic, carbocyclic or aromatic functional group.
- the quaternary compound is selected from the group consisting of tetraethylphosphonium hydroxide, tetra-n-butylphosphonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n- octylphosphonium hydroxide, and tetraphenylphosphonium hydroxide.
- the neutralization step is carried out such that the temperature of the reaction mixture is maintained at about 10 C to about 50 C in one embodiment, and at about 20 C to about 30 C in another embodiment. In another embodiment the reaction is carried out at autogenous temperature.
- the neutralization process is conveniently carried out by monitoring the pH of the nuetralization mixture. In one embodiment, the pH of the neutralization mixture is about 4 to about 6, while in another embodiment, the pH is about 5 to about 5.5.
- the quaternary onium organosilicon sulfonate obtained from the neutralization step is extracted out of the product mixture by using a suitable solvent.
- suitable solvents include those that dissolve the quaternary onium organosilicon compound.
- suitable solvents comprise halogenated aliphatic and aromatic compounds, aliphatic and aromatic hydrocarbons, cyclic and acylic ethers, and mixtures thereof.
- a suitable solvent for extraction is chloroform.
- substantially all the solvent is removed.
- substantially means an amount which is greater than 90 weight percent (wt.%) removed, in other embodiments, greater than about 98 wt.%) removed, in still other embodiments, greater than about 99 wt. % removed, based on the weight of solvent used.
- removal of substantially all the solvent means that no more condensate is obtained in the evaporation process.
- the general method described above is applicable for preparing any of the quaternary onium organosilicon compounds described above.
- the general method is used for preparing tetra-n-butylphosphonium 3- trimethylsilylpropanesulfonate.
- the solution comprising water and sodium 3- trimethylsilylpropanesulfonate, used for carrying out the sodium ion-hydrogen ion exchange can also comprise C]-C aliphatic alcohols, tetrahydrofuran, acetonitrile, C 7 -C 9 aromatic hydrocarbons, and mixtures thereof.
- the solvent used for extraction of the product in various embodiments comprises halogenated aliphatic and aromatic compounds, aliphatic and aromatic hydrocarbons, cyclic and acylic ethers, and mixtures thereof. Evaporation of the solvent from the extract to isolate the final product can be accomplished under atmospheric pressure or under sub-atmospheric pressure.
- the quaternary onium organosilicon compounds depicted hereinabove have high surface migratory aptitude in polymeric compositions that aids in fast dissipation of localized static charge accumulated on a polymer surface. These compounds possess a polar, hydrophilic onium sulfonate group, and a non-polar, hydrophobic moiety. Although the invention is not limited by any theory of operation, it is believed that the silicon containing hydrophobic moiety enhances migratory aptitude and the polar group attracts ambient moisture to form a layer of water molecules on the polymer surface. These water molecules in turn are hydrogen bonded to each other. Dissipation of localized surface charge occurs through this hydrogen-bonded layer of water molecules, thus leading to antistatic activity.
- the quaternary onium organosilicon compounds have high thermal stability based on thermogravimetric analyses (hereinafter referred to as "TGA"). TGA studies show that these compounds do not undergo any significant thermal decomposition even at temperatures of greater than about 300 ° C, conditions which are generally used for processing polymers. The thermal stability characteristics are comparable to that of tetra-n-butylphosphonium 4-dodecylbenzene sulfonate (CAS: 111503-99-2; commercially available as EPA 202 from Takemoto Oil & Fat Co., Ltd.). Another important characteristic of quaternary onium organosilicon compounds is that they do not adversely affect the physical properties of the compositions to which they are added, such as glass transition temperature of the resulting polymeric compositions.
- the quaternary onium organosilicon compounds described above are valuable as antistatic additives for any polymer. Thus they can be used in thermoplastic as well as thermoset polymer compositions.
- the polymers that can be used comprise condensation and addition polymers.
- the amount of the quaternary onium organosilicon compound can vary.
- Polymer compositions typically comprise the quaternary onium organosilicon compound in amounts of about 2.5 X 10 "" parts to about 6 parts per 100 parts of the polymer in one embodiment, about 3 X 10 "2 parts to about 6 parts per 100 parts of polymer in a second embodiment, and about 0.5 parts to about 6 parts per 100 parts of polymer in a third embodiment.
- Preferred quaternary onium organosilicon compounds are tetra-n-butylphosphonium 3- trimethylsilylpropanesulfonate, tetra-n-butylammonium 3- trimethylsilylpropanesulfonate, and mixtures thereof.
- thermoplastic polymers comprises aromatic polycarbonate, polyestercarbonate, polyphenylene sulfide, polyetherimide, polyester, liquid crystalline polyester, polystyrene, polyphenylene ether, polyphenylene ether/styrene polymer blends, polyamide, polyketone, acrylonitrile-butadiene-styrene copolymer, styrene- acrylonitrile copolymer, polyolefm, polyethylene, polypropylene, polyacetal, blends thereof, and blends thereof with other materials, such as for example, glass.
- Preferred thermoplastic polymers are polycarbonates and polyestercarbonates obtained from polymerization processes, which include melt transesterification, interfacial polymerization, solid state polymerization, and solution and redistribution processes, or combinations thereof.
- the polymer composition may further comprise materials such as antioxidants, thermal stabilizers, ultraviolet stabilizers, processing agents, mold release agents, fillers, and flame retardants.
- the antistatic polymer compositions may be made using methods known in the art.
- the polymer compositions may be made by methods comprising steps, at least one step of which comprises dry-blending the quaternary onium organosilicon compound with pellets or powder of the thermoplastic resin to produce a polymer composition, melt blending the quaternary onium organosilicon compound with polymer resin in a melt process or solution blending the quaternary onium organosilicon compound with the polymer resin. These techniques are known in the art.
- Dry blending represents the process of preparing the polymer composition by mixing all the necessary ingredients before the blended mixture is subjected to a polymer processing step for making articles. Dry blending is performed using techniques that are well known to one skilled in the art.
- the polymer resin component of the feed is either in a pellet form, powder form, or both. In a particular embodiment the polymer resin component of the feed is in powder form.
- the feed for the blending process may also include other materials as additives, as previously described.
- Another method of making the polymer composition involves combining the ingredients in melt.
- a solvent is optionally used to aid in mixing with the rest of the feed mixture.
- the processing equipment may have a devolatilization system to effectively remove volatiles such as solvent during the processing step.
- Any convenient type of melt processing equipment may be employed and those skilled in the art may choose appropriate equipment without undue experimentation depending upon such factors as the type of polymer to be processed.
- suitable melt processing equipment includes, but is not limited to, extruders, kneaders, roll-mills and similar equipment.
- the polymer composition may be formed into articles or coatings using any methods known in the art such as injection molding, sheet molding, thermoforming, blow molding, and spray coating.
- the antistatic compositions find a variety of uses in such applications as in forward lighting assemblies, automotive headlamp lenses, fog lamp lenses, ophthalmic devices, conveyor belt systems, printer devices, and display panel devices for appliances.
- This example describes the preparation of tetra-n-butylphosphonium 3- trimethylsilylpropanesulfonate .
- Tulsion T-42 MP(H + ) an acidic gel type ion exchange resin was purchased from Thermax Company, India.
- the resin had moisture content of about 50-52 % and an exchange capacity of about 1.8 milliequivalents of H + per unit volume of resin in the wet state (about 4.9 milliequivalents of H + per unit volume of resin in the dry state).
- the water solution of the free 3-(trimethylsilyl)-l-propanesulfonic acid thus obtained was neutralized with tetra-n-butylphosphonium hydroxide until the pH of the solution was about 5 to 5.5.
- the resulting mixture was extracted with chloroform (three times) and the combined chloroform washes was washed with water (three times).
- the chloroform layer was separated, dried with anhydrous sodium sulfate, and concentrated under reduced pressure to remove solvent and other volatiles.
- the residual material was finally dried at 40°C and 0.1 mm Hg to afford tetra-n-butylphosphonium 3-(trimethylsilyl)-l -propanesulfonate as a white solid.
- the yield of the product was 26.9 grams, or 99% of the theoretical amount. Proton NMR spectrum of the compound indicated that it was the desired compound.
- This example describes the preparation of tetra-n-butylammonium 3- trimethyl silylpropanesulfonate .
- the water solution of the free 3-(trimethylsilyl)-l-propanesulfonic acid thus obtained was neutralized with tetra-n-butylammonium hydroxide until the pH of the solution was about 5 to 5.5.
- the resulting mixture was extracted with chloroform (three times) and the combined chloroform washes was washed with water (three times).
- the chloroform layer was separated, dried with anhydrous sodium sulfate, and concentrated under reduced pressure to remove solvent and other volatiles.
- the residual material was finally dried at 40 °C and 0.1 mm Hg to afford tetra-n- butylammonium 3-(trimethylsilyl)-l -propanesulfonate as a hygroscopic white solid.
- the yield of the product was 17.4 grams, or 97% of the theoretical amount. Proton NMR spectrum of the compound indicated that it was the desired compound.
- the aromatic polycarbonate resin used in the examples was a bisphenol A (hereinafter referred to as "BPA") homopolycarbonate resin having an intrinsic viscosity of about 0.46 deciliters per gram, as measured in dichloromethane at 20 C.
- BPA bisphenol A
- the polycarbonate was melt-blended with 15 grams of antistatic and/or antidust agent per kilogram of the molding mixture.
- the molding mixture also contained 2.7 grams of silicone oil mold release agent per kilogram of molding mixture and 3.9 grams of stabilizers per kilogram of molding mixture, which are not believed to affect the antistatic properties.
- the molding mixture was molded in a 25 mm twin-screw extruder using an operating temperature of about 285 C.
- the resulting strands were quenched in water and cut into pellets, which were dried at about 120 C for about 2 h.
- the dried pellets were injection molded using a single screw injection- molding machine to produce 10 cm square plaques having a thickness of about 2.5 mm.
- the maximum temperature for the injection-molding barrel was about 285 C.
- plaques required for carrying out the static decay tests were obtained from the larger plaques prepared above. Each plaque used for the static decay test measured about 78 mm X 58 mm X 2.5 mm. Prior to the test, the plaques were conditioned at a temperature of about 23 C and a relative humidity of about 50% for about three days. The static decay tests were carried out on these plaques using a Static Honestmeter, Model S-5109 instrument manufactured by Shishido Electrostatic Ltd. The applied voltage was cut-off when the surface charge attained a fixed value of about 3 kilovolts. Subsequently, the decay of surface charge was followed with time with a detector.
- the static half decay time (indicated by "Tj /2 ”) represents the time at which the surface charge reached a value that was half the initial value.
- Tj glass transition temperatures
- %T Percent transmission
- the quaternary onium organosilicon compound shows significantly better dissipation of surface charge of a polymeric composition without significantly affecting the glass transition temperature.
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- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60322565T DE60322565D1 (en) | 2002-08-06 | 2003-06-17 | ANTISTATIC AND DERIVED POLYMER COMPOSITIONS |
EP03766822A EP1556437B1 (en) | 2002-08-06 | 2003-06-17 | Antistatic agents and polymer compositions derived therefrom |
AU2003247597A AU2003247597A1 (en) | 2002-08-06 | 2003-06-17 | Antistatic agents and polymer compositions derived therefrom |
JP2004526002A JP2005535690A (en) | 2002-08-06 | 2003-06-17 | Antistatic agent and polymer composition obtained from said antistatic agent |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/064,676 US6900257B2 (en) | 2002-08-06 | 2002-08-06 | Antistatic agents and polymer compositions derived therefrom |
US10/064,676 | 2002-08-06 |
Publications (1)
Publication Number | Publication Date |
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WO2004013218A1 true WO2004013218A1 (en) | 2004-02-12 |
Family
ID=31493933
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2003/019602 WO2004013218A1 (en) | 2002-08-06 | 2003-06-17 | Antistatic agents and polymer compositions derived therefrom |
Country Status (11)
Country | Link |
---|---|
US (1) | US6900257B2 (en) |
EP (1) | EP1556437B1 (en) |
JP (1) | JP2005535690A (en) |
KR (1) | KR20050062767A (en) |
CN (1) | CN100341928C (en) |
AT (1) | ATE402977T1 (en) |
AU (1) | AU2003247597A1 (en) |
DE (1) | DE60322565D1 (en) |
ES (1) | ES2306896T3 (en) |
TW (1) | TW200402444A (en) |
WO (1) | WO2004013218A1 (en) |
Cited By (3)
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WO2007015165A1 (en) | 2005-06-02 | 2007-02-08 | Nalco Company | Compositions comprising (poly) alpha olefins |
EP2730582A4 (en) * | 2011-07-04 | 2015-03-04 | Nisshinbo Holdings Inc | Ionic liquid |
WO2017183342A1 (en) * | 2016-04-21 | 2017-10-26 | 日清紡ホールディングス株式会社 | Silicon-containing sulfuric acid ester salt |
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US6841598B2 (en) * | 2002-08-16 | 2005-01-11 | General Electric Company | Antistatic and antidust agents, compositions thereof, and methods of manufacture |
JP4532479B2 (en) * | 2003-03-31 | 2010-08-25 | 東京エレクトロン株式会社 | A barrier layer for a processing member and a method of forming the same. |
US20080119598A1 (en) * | 2005-01-14 | 2008-05-22 | E.I. Du Pont De Nemours And Company | Treated Inorganic Metal Containing Powders and Polymer Films Containing Them |
JP6051757B2 (en) * | 2012-10-16 | 2016-12-27 | 日清紡ホールディングス株式会社 | Ionic liquid |
JP6090561B2 (en) * | 2012-10-16 | 2017-03-08 | 日清紡ホールディングス株式会社 | Electrolyte salt and electrolyte for power storage device, and power storage device |
CN105518055A (en) | 2013-06-03 | 2016-04-20 | 普立万公司 | Low molecular weight polyphenylene ether prepared without solvents |
US10619117B2 (en) | 2015-05-11 | 2020-04-14 | Nisshinbo Holdings Inc. | Lubricant including silicon-containing ionic liquid |
JP6582705B2 (en) * | 2015-08-10 | 2019-10-02 | 日清紡ホールディングス株式会社 | Use of compounds exhibiting lower critical eutectic temperature type phase behavior |
JP6601094B2 (en) * | 2015-09-25 | 2019-11-06 | 日清紡ホールディングス株式会社 | Additive for electrolyte |
JP6958511B2 (en) * | 2018-08-17 | 2021-11-02 | 信越化学工業株式会社 | Organopolysiloxane compound, a method for producing the same, an antistatic agent containing the same, and a curable composition. |
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-
2003
- 2003-06-17 CN CNB038236907A patent/CN100341928C/en not_active Expired - Fee Related
- 2003-06-17 AU AU2003247597A patent/AU2003247597A1/en not_active Abandoned
- 2003-06-17 JP JP2004526002A patent/JP2005535690A/en active Pending
- 2003-06-17 KR KR1020057002247A patent/KR20050062767A/en not_active Application Discontinuation
- 2003-06-17 ES ES03766822T patent/ES2306896T3/en not_active Expired - Lifetime
- 2003-06-17 AT AT03766822T patent/ATE402977T1/en not_active IP Right Cessation
- 2003-06-17 DE DE60322565T patent/DE60322565D1/en not_active Expired - Fee Related
- 2003-06-17 EP EP03766822A patent/EP1556437B1/en not_active Expired - Lifetime
- 2003-06-17 WO PCT/US2003/019602 patent/WO2004013218A1/en active Application Filing
- 2003-07-29 TW TW092120685A patent/TW200402444A/en unknown
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GB1030888A (en) * | 1963-12-05 | 1966-05-25 | Dow Corning | Silanes and siloxanes |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007015165A1 (en) | 2005-06-02 | 2007-02-08 | Nalco Company | Compositions comprising (poly) alpha olefins |
EP1885784B1 (en) * | 2005-06-02 | 2014-08-13 | Nalco Company | Compositions comprising (poly) alpha olefins |
EP2730582A4 (en) * | 2011-07-04 | 2015-03-04 | Nisshinbo Holdings Inc | Ionic liquid |
WO2017183342A1 (en) * | 2016-04-21 | 2017-10-26 | 日清紡ホールディングス株式会社 | Silicon-containing sulfuric acid ester salt |
JP2017193510A (en) * | 2016-04-21 | 2017-10-26 | 日清紡ホールディングス株式会社 | Silicon-containing sulfate ester salt |
KR20180136947A (en) * | 2016-04-21 | 2018-12-26 | 닛신보 홀딩스 가부시키 가이샤 | The silicon-containing sulfuric acid ester salt |
US10494393B2 (en) | 2016-04-21 | 2019-12-03 | Nisshinbo Holdings, Inc. | Silicon-containing sulfuric acid ester salt |
KR102285191B1 (en) | 2016-04-21 | 2021-08-03 | 닛신보 홀딩스 가부시키 가이샤 | Silicon-containing sulfuric acid ester salt |
Also Published As
Publication number | Publication date |
---|---|
US20040030015A1 (en) | 2004-02-12 |
EP1556437B1 (en) | 2008-07-30 |
DE60322565D1 (en) | 2008-09-11 |
EP1556437A1 (en) | 2005-07-27 |
JP2005535690A (en) | 2005-11-24 |
CN1688644A (en) | 2005-10-26 |
KR20050062767A (en) | 2005-06-27 |
TW200402444A (en) | 2004-02-16 |
CN100341928C (en) | 2007-10-10 |
ES2306896T3 (en) | 2008-11-16 |
AU2003247597A1 (en) | 2004-02-23 |
ATE402977T1 (en) | 2008-08-15 |
US6900257B2 (en) | 2005-05-31 |
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