KR20220039729A - Silicon isocyanate compound-containing composition and method for producing the same - Google Patents
Silicon isocyanate compound-containing composition and method for producing the same Download PDFInfo
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- KR20220039729A KR20220039729A KR1020227003738A KR20227003738A KR20220039729A KR 20220039729 A KR20220039729 A KR 20220039729A KR 1020227003738 A KR1020227003738 A KR 1020227003738A KR 20227003738 A KR20227003738 A KR 20227003738A KR 20220039729 A KR20220039729 A KR 20220039729A
- Authority
- KR
- South Korea
- Prior art keywords
- silicon
- isocyanate compound
- compound
- solvent
- silicon isocyanate
- Prior art date
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- -1 Silicon isocyanate compound Chemical class 0.000 title claims abstract description 177
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000012948 isocyanate Substances 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 30
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 13
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000012686 silicon precursor Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 description 30
- 230000018044 dehydration Effects 0.000 description 23
- 238000006297 dehydration reaction Methods 0.000 description 23
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 19
- 230000008569 process Effects 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 10
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical group 0.000 description 7
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 7
- UVVUGWBBCDFNSD-UHFFFAOYSA-N tetraisocyanatosilane Chemical class O=C=N[Si](N=C=O)(N=C=O)N=C=O UVVUGWBBCDFNSD-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920001515 polyalkylene glycol Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229940057995 liquid paraffin Drugs 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DFJSZWHUOKADCX-UHFFFAOYSA-N triisocyanato(methyl)silane Chemical compound O=C=N[Si](C)(N=C=O)N=C=O DFJSZWHUOKADCX-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 239000005055 methyl trichlorosilane Substances 0.000 description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003118 aryl 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 150000001913 cyanates Chemical class 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- UCKORWKZRPKRQE-UHFFFAOYSA-N bromo(triethyl)silane Chemical compound CC[Si](Br)(CC)CC UCKORWKZRPKRQE-UHFFFAOYSA-N 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SRIHMZCTDWKFTQ-UHFFFAOYSA-N dibromo(diethyl)silane Chemical compound CC[Si](Br)(Br)CC SRIHMZCTDWKFTQ-UHFFFAOYSA-N 0.000 description 1
- LIQOCGKQCFXKLF-UHFFFAOYSA-N dibromo(dimethyl)silane Chemical compound C[Si](C)(Br)Br LIQOCGKQCFXKLF-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- IPYLPYVDNXWYSR-UHFFFAOYSA-N diethyl(diisocyanato)silane Chemical compound O=C=N[Si](CC)(CC)N=C=O IPYLPYVDNXWYSR-UHFFFAOYSA-N 0.000 description 1
- ICFCQEJDICSLOV-UHFFFAOYSA-N diisocyanato(dimethyl)silane Chemical compound O=C=N[Si](C)(C)N=C=O ICFCQEJDICSLOV-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- SHVHLTQVSHXYFA-UHFFFAOYSA-N ethyl(triisocyanato)silane Chemical compound O=C=N[Si](CC)(N=C=O)N=C=O SHVHLTQVSHXYFA-UHFFFAOYSA-N 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIZHERJWXFHGGU-UHFFFAOYSA-N isocyanato(trimethyl)silane Chemical compound C[Si](C)(C)N=C=O NIZHERJWXFHGGU-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- POMZBEGASDKMRR-UHFFFAOYSA-M lithium;cyanate Chemical compound [Li+].[O-]C#N POMZBEGASDKMRR-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- DMAZIRSKQBAGAH-UHFFFAOYSA-N tetraisocyanatostannane Chemical class [Sn+4].[N-]=C=O.[N-]=C=O.[N-]=C=O.[N-]=C=O DMAZIRSKQBAGAH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- KVENDAGPVNAYLY-UHFFFAOYSA-N tribromo(ethyl)silane Chemical compound CC[Si](Br)(Br)Br KVENDAGPVNAYLY-UHFFFAOYSA-N 0.000 description 1
- KBSUPJLTDMARAI-UHFFFAOYSA-N tribromo(methyl)silane Chemical compound C[Si](Br)(Br)Br KBSUPJLTDMARAI-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- VIGRJDWPNTXJSQ-UHFFFAOYSA-N triethyl(isocyanato)silane Chemical compound CC[Si](CC)(CC)N=C=O VIGRJDWPNTXJSQ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- 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
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
Abstract
규소이소시아네이트 화합물의 단량체의 순도가 높은 규소이소시아네이트 화합물 함유 조성물을, 산업 레벨에서 저비용으로 제조하는 방법을 제공한다. 하기 공정 (A) 내지 공정 (D) 를 갖는 방법에 의해, 할로겐화규소 화합물과 시안산염 또는 이소시안산염을, 용매 및 알킬렌글리콜계 화합물의 존재하에서 반응시킴으로써, 규소이소시아네이트 화합물 함유 조성물을 제조한다. (A) 그 시안산염 또는 이소시안산염과, 공비 용제와, 그 알킬렌글리콜계 화합물과, 그 용매를 혼합시켜 액을 생성시키는 공정 (B) 그 액을 가열하여, 물과 그 공비 용제를 제거하는 공정 (C) 그 액에 그 할로겐화규소 화합물을 첨가하여 그 규소이소시아네이트 화합물을 생성시키는 공정 (D) 그 액을 가열하여 그 규소이소시아네이트 화합물을 유거하여 회수하는 공정A method for producing a silicon isocyanate compound-containing composition having a high purity of the monomer of the silicon isocyanate compound at an industrial level at low cost is provided. A silicon isocyanate compound-containing composition is prepared by reacting a silicon halide compound with a cyanate or isocyanate in the presence of a solvent and an alkylene glycol compound by a method having the following steps (A) to (D). (A) The cyanate or isocyanate, the azeotropic solvent, the alkylene glycol-based compound, and the solvent are mixed to form a solution (B) The solution is heated to remove water and the azeotropic solvent Step (C) Step of adding the silicon halide compound to the liquid to produce the silicon isocyanate compound (D) Step of heating the liquid and distilling the silicon isocyanate compound to recover
Description
본 발명은, 규소이소시아네이트 화합물 함유 조성물의 제조 방법에 관한 것으로서, 보다 상세하게는, 공비 용제를 사용하여 탈수 공정을 실시하는 것을 특징으로 한 규소이소시아네이트 화합물 함유 조성물의 제조 방법에 관한 것이다.The present invention relates to a method for producing a composition containing a silicon isocyanate compound, and more particularly, to a method for producing a composition containing a silicon isocyanate compound characterized by performing a dehydration step using an azeotropic solvent.
규소이소시아네이트 화합물은, 예를 들어 알코올이나 제 1 아민, 제 2 아민, 카르복실산 등의 활성 수소를 분자 중에 포함하는 화합물과 용이하게 반응하기 때문에, 폴리머의 개질제로서 사용된다. 또한, 규소이소시아네이트 화합물은, 중합물의 성분으로서 용이하게 도입할 수 있어, 규소의 특성을 공업 재료에 부가할 수 있다. 또한, 규소이소시아네이트 화합물은, 물과 신속하게 반응하는 것으로부터, 공기 중의 수분, 또는, 유리, 세라믹스, 금속 등의 표면에 존재하는 흡착수 등과 반응하여, 밀착성이 높은 규소산화물 피막을 형성시킬 수 있다.A silicon isocyanate compound is used as a polymer modifier because it reacts easily with a compound containing active hydrogen in a molecule|numerator, such as alcohol, a primary amine, a secondary amine, and carboxylic acid, for example. Moreover, a silicon isocyanate compound can be easily introduce|transduced as a component of a polymer, and can add the characteristic of silicon to an industrial material. In addition, since the silicon isocyanate compound reacts rapidly with water, it reacts with moisture in the air, or adsorbed water present on the surface of glass, ceramics, metal, etc., to form a silicon oxide film with high adhesion.
규소이소시아네이트 화합물의 제조 방법으로는, 용제 존재하에서 Si-X (X 는 할로겐을 나타낸다) 결합을 갖는 할로겐화실란 화합물과 시안산염 또는 이소시안산염을, 알킬아민, 니트로알칸 또는 크라운 에테르의 존재하에서 반응시켜 제조하는 방법 (특허문헌 1) 이나, 할로겐화실란 화합물과 시안산염 또는 이소시안산염을, 알킬렌글리콜 화합물의 존재하에서 반응시켜 제조하는 방법 (특허문헌 2) 이 알려져 있다.As a method for producing a silicon isocyanate compound, a halogenated silane compound having a Si-X (X represents halogen) bond and a cyanate or isocyanate are reacted in the presence of an alkylamine, nitroalkane or crown ether in the presence of a solvent. A manufacturing method (patent document 1) and a manufacturing method (patent document 2) are known by making a halogenated silane compound and a cyanate or isocyanate react in presence of an alkylene glycol compound.
또한, 헥사오르가노디실라잔을, 염화철의 존재하에서, 탄산 가스와 반응시켜 제조하는 방법 (특허문헌 3), 트리클로로실란과 시안산알칼리를, 아세토니트릴을 소량 함유하는 유기 용매 중에서 반응시켜 제조하는 방법 (특허문헌 4), 유기 주석이소시아네이트류와, 활성 할로겐 원자를 갖는 유기 규소 화합물을 반응시켜 제조하는 방법 (특허문헌 5) 이 알려져 있다.In addition, a method for producing hexaorganodisilazane by reacting it with carbon dioxide gas in the presence of iron chloride (Patent Document 3), trichlorosilane and alkali cyanate in an organic solvent containing a small amount of acetonitrile. A method (patent document 4) and a method (patent document 5) in which organic tin isocyanates are reacted with an organosilicon compound having an active halogen atom are known.
한편, 규소이소시아네이트 화합물은, 물과의 반응에 의해, 다이머 화합물이나 올리고머 화합물을 형성하는 것이 알려져 있고 (예를 들어, 특허문헌 6), 반응계에 물이 혼입되었을 경우, 규소이소시아네이트 화합물 (의 모노머) 의 순도 저하로 연결된다.On the other hand, it is known that a silicon isocyanate compound forms a dimer compound or an oligomer compound by reaction with water (for example, Patent Document 6), and when water is mixed in the reaction system, the silicon isocyanate compound (monomer of) leads to a decrease in the purity of
이 때문에, 고순도의 규소이소시아네이트 화합물의 모노머를 얻기 위해서는, 원료가 되는 화합물로부터 물을 충분히 제거할 필요가 있다.For this reason, in order to obtain the monomer of a high-purity silicon isocyanate compound, it is necessary to fully remove water from the compound used as a raw material.
특허문헌 2 의 실시예에 있어서는, 탈수한 시안산염이나 이소시안산염을 사용하여 규소이소시아네이트 화합물을 제조하고 있지만, 사용하는 용제나 알킬렌글리콜과 같은 반응에 사용하는 다른 화합물의 탈수를 실시하지 않는 한, 할로겐화실란 화합물이 시안산염 또는 이소시안산염과 반응하기 전에, 함유하는 물과 반응하게 된다.In the Example of Patent Document 2, a silicon isocyanate compound is produced using dehydrated cyanate or isocyanate, but unless dehydration of another compound used in the reaction such as a solvent or alkylene glycol is performed. , before the halogenated silane compound reacts with the cyanate or isocyanate, it reacts with the water it contains.
시안산염 또는 이소시안산염의 탈수 방법으로서, 감압하에서 직화로 가열하여 탈수하는 방법이 알려져 있지만, 가열하여 탈수하는 공정과 반응 공정의 2 회의 공정을 거칠 필요가 있다. 또한, 산업 레벨에서의 실시를 고려했을 경우, 제조 가마를 직화로 가열하여 제조하는 공정으로 제조하는 것은 곤란하다. 나아가서는, 균일하게 탈수된 시안산염 또는 이소시안산염을 얻는 것이 어렵다.As a method of dehydration of cyanate or isocyanate, a method of dehydration by heating under a direct fire under reduced pressure is known. In addition, when implementation at the industrial level is considered, it is difficult to manufacture by a process of heating a manufacturing kiln by direct fire. Furthermore, it is difficult to obtain uniformly dehydrated cyanate or isocyanate.
또한, 특허문헌 2 의 방법에 있어서, 반응 촉진제, 용제에 대하여 직화로 가열했을 경우, 열 분해를 회피하면서 탈수하는 것은 곤란하다.Moreover, in the method of patent document 2, when heating with direct fire with respect to a reaction promoter and a solvent, it is difficult to dehydrate, avoiding thermal decomposition.
그 밖의 탈수 방법으로는, 몰레큘러 시브스, 활성 백토, 실리카 겔 등의 고체 흡착제를 사용한 탈수 방법을 들 수 있다. 그러나, 시안산염 또는 이소시안산염, 반응 촉진제, 용제로 이루어지는 용액은 슬러리 상태이며, 이 혼합 용액으로부터 고체 흡착제만을 분리하는 것이 곤란하다. 고체 흡착제가 잔존한 상태에서 할로겐화실란 화합물과 반응시켰을 경우, 고체 흡착제에 포함되는 물과 반응하여, 수율 및/또는 순도의 저하로 연결된다.As another dehydration method, the dehydration method using solid adsorbents, such as molecular sieves, activated clay, and silica gel, is mentioned. However, a solution comprising cyanate or isocyanate, a reaction accelerator, and a solvent is in a slurry state, and it is difficult to separate only the solid adsorbent from the mixed solution. When the solid adsorbent is reacted with the halogenated silane compound while the solid adsorbent remains, it reacts with water contained in the solid adsorbent, leading to a decrease in yield and/or purity.
보다 고품질의 규소 산화물 피막을 얻기 위해서, 단량체의 순도가 높은 규소이소시아네이트 화합물 함유 조성물이 요구되고 있고, 이러한 규소이소시아네이트 화합물 함유 조성물을 제조하기 위한 새로운 제조 방법의 개발이 요구되고 있다.In order to obtain a higher quality silicon oxide film, a composition containing a silicon isocyanate compound with high monomer purity is required, and development of a new manufacturing method for manufacturing such a composition containing a silicon isocyanate compound is required.
본 발명은 상기 배경 기술을 감안하여 이루어진 것으로서, 그 과제는, 규소이소시아네이트 화합물의 단량체의 순도가 높은 규소이소시아네이트 화합물 함유 조성물을 제조할 수 있는 방법으로, 산업 레벨에서의 실시가 가능하고, 저비용으로 규소이소시아네이트 화합물 함유 조성물을 제조할 수 있는 방법을 제공하는 것에 있다.The present invention has been made in view of the above background art, and its object is a method capable of producing a silicon isocyanate compound-containing composition having a high purity of the monomer of the silicon isocyanate compound, which can be implemented at an industrial level and can be implemented at a low cost It is to provide the method which can manufacture an isocyanate compound containing composition.
본 발명자는, 상기의 과제를 해결하기 위하여 예의 검토를 거듭한 결과, 할로겐화실란 화합물과 시안산염 또는 이소시안산염을, 알킬렌글리콜 화합물의 존재하에서 반응시켜 규소이소시아네이트 화합물 함유 조성물을 제조하는 방법에 있어서, 할로겐화실란 화합물을 첨가하기 전에, 시안산염 또는 이소시안산염과 알킬렌글리콜 화합물을 함유하는 액에, 공비 용제를 첨가하여, 그 공비 용제와 물의 공비에 의한 탈수 공정을 실시함으로써, 종래의 제조 방법에 있어서 문제가 되고 있던, 물의 혼입에 의한 규소이소시아네이트 화합물 단량체의 순도 저하의 문제를 해결할 수 있는 것을 알아내고, 본 발명을 완성하기에 이르렀다.The present inventors, as a result of repeated intensive studies to solve the above problems, reacted a halogenated silane compound with a cyanate or isocyanate in the presence of an alkylene glycol compound to prepare a composition containing a silicon isocyanate compound, , a conventional manufacturing method by adding an azeotropic solvent to a liquid containing cyanate or isocyanate and an alkylene glycol compound before adding the halogenated silane compound, and performing a dehydration step by azeotropically mixing the azeotropic solvent with water. found that the problem of a decrease in the purity of the silicon isocyanate compound monomer due to mixing of water, which had been a problem in the present invention, could be solved, and the present invention was completed.
즉, 본 발명은, 할로겐화규소 화합물과 시안산염 또는 이소시안산염을, 용매 및 알킬렌글리콜계 화합물의 존재하에서 반응시킴으로써 규소이소시아네이트 화합물을 생성시키는 규소이소시아네이트 화합물 함유 조성물의 제조 방법으로서 하기 공정 (A) 내지 공정 (D) 까지를 갖는 것을 특징으로 하는 규소이소시아네이트 화합물 함유 조성물의 제조 방법을 제공하는 것이다.That is, the present invention relates to a method for producing a silicon isocyanate compound-containing composition in which a silicon isocyanate compound is produced by reacting a silicon halide compound with a cyanate or isocyanate in the presence of a solvent and an alkylene glycol compound, the following step (A) To provide a method for producing a composition containing a silicon isocyanate compound, comprising steps (D).
(A) 그 시안산염 또는 이소시안산염과, 공비 용제와, 그 알킬렌글리콜계 화합물과, 그 용매를 혼합시켜 액을 생성시키는 공정(A) A step of mixing the cyanate or isocyanate, the azeotropic solvent, the alkylene glycol compound, and the solvent to produce a liquid
(B) 그 액을 가열하여, 물과 그 공비 용제를 제거하는 공정(B) a step of heating the liquid to remove water and its azeotropic solvent
(C) 그 액에 그 할로겐화규소 화합물을 첨가하여 그 규소이소시아네이트 화합물을 생성시키는 공정(C) A step of adding the silicon halide compound to the solution to produce the silicon isocyanate compound
(D) 그 액을 가열하여 그 규소이소시아네이트 화합물을 유거하여 회수하는 공정(D) a step of heating the liquid to distill off and recover the silicon isocyanate compound
또한, 본 발명은, 규소이소시아네이트 화합물을 80 질량％ 이상 함유하는 것을 특징으로 하는 규소이소시아네이트 화합물 함유 조성물을 제공하는 것이다.Moreover, this invention contains 80 mass % or more of silicon isocyanate compounds, It is providing the silicon isocyanate compound containing composition characterized by the above-mentioned.
또한, 본 발명은, 상기의 규소이소시아네이트 화합물 함유 조성물의 제조 방법으로 제조한 규소이소시아네이트 화합물 함유 조성물을 규소 전구체로서 사용하는 것을 특징으로 하는 규소 산화물 또는 규소 산화물 피막의 제조 방법을 제공하는 것이다.Further, the present invention provides a method for producing a silicon oxide or silicon oxide film, wherein the silicon isocyanate compound-containing composition produced by the method for producing a silicon isocyanate compound-containing composition described above is used as a silicon precursor.
본 발명에 의하면, 규소이소시아네이트 화합물의 단량체의 순도가 높은 규소이소시아네이트 화합물 함유 조성물의 제조 방법을 제공할 수 있다. 구체적으로는, 본 발명에서는, 정제를 실시하기 전의 단계에서 규소이소시아네이트 화합물의 단량체의 순도가 80 질량％ 이상인 규소이소시아네이트 화합물 함유 조성물을 제공할 수 있다.ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the silicon isocyanate compound containing composition with high purity of the monomer of a silicon isocyanate compound can be provided. Specifically, in the present invention, it is possible to provide a composition containing a silicon isocyanate compound in which the purity of the monomer of the silicon isocyanate compound is 80% by mass or more in the stage before purification.
또한, 본 발명의 방법은, 산업 레벨에서의 실시가 가능하고, 저비용으로 규소이소시아네이트 화합물 함유 조성물을 제조할 수 있다.Moreover, the method of this invention can be implemented at an industrial level, and a silicon isocyanate compound containing composition can be manufactured at low cost.
이하, 본 발명에 대하여 설명하지만, 본 발명은 이하의 실시형태로 한정되는 것이 아니고, 임의로 변형하여 실시할 수 있다.EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated, this invention is not limited to the following embodiment, It can deform|transform arbitrarily and implement it.
본 발명의 규소이소시아네이트 화합물 함유 조성물의 제조 방법은, 할로겐화규소 화합물과 시안산염 또는 이소시안산염을, 용매 및 알킬렌글리콜계 화합물의 존재하에서 반응시킴으로써 규소이소시아네이트 화합물을 생성시킨다.In the method for producing a composition containing a silicon isocyanate compound of the present invention, a silicon isocyanate compound is produced by reacting a silicon halide compound with a cyanate or isocyanate in the presence of a solvent and an alkylene glycol compound.
＜규소이소시아네이트 화합물＞<Silicon isocyanate compound>
「규소이소시아네이트 화합물」 이란, 규소 (Si) 와 이소시아네이트기 (-N=C=O) 가 직접 결합한 화합물 전반을 말한다.The "silicon isocyanate compound" refers to the general compound in which silicon (Si) and an isocyanate group (-N=C=O) are directly bonded.
규소이소시아네이트 화합물 중, 특히, 분자 내에 규소 원자를 1 개만 갖는 것, 즉, 규소이소시아네이트 화합물의 단량체 (모노머) 는, 본 발명의 제조 방법으로 제조하는 데에 적합하다.Among the silicon isocyanate compounds, in particular, those having only one silicon atom in the molecule, that is, the monomer (monomer) of the silicon isocyanate compound, are suitable for production by the production method of the present invention.
이러한 규소이소시아네이트 화합물의 단량체의 예로는, 하기 식 (1) 로 나타내는 것을 들 수 있다.As an example of the monomer of such a silicon isocyanate compound, what is represented by following formula (1) is mentioned.
Rn(OR)mSi(NCO)4-n-m (1)R n (OR) m Si(NCO) 4-nm (1)
식 (1) 에 있어서, R 은 치환되어 있어도 되는 탄화수소기이고, R 이 복수 존재하는 경우, 각각의 R 은 상이해도 된다. n 및 m 은 각각 0 이상 3 이하의 정수이며, n 과 m 의 합은, 0 이상 3 이하의 정수이다.In Formula (1), R is an optionally substituted hydrocarbon group, and when two or more R exist, each R may differ. n and m are each an integer of 0 or more and 3 or less, and the sum of n and m is an integer of 0 or more and 3 or less.
R 은, 포화여도 되고, 불포화여도 되고, 방향족 고리를 가지고 있어도 된다. R 의 구체예로는, 메틸기, 에틸기, 프로필기, 부틸기, 옥틸기, 데실기, 스테아릴기, 베헤닐기, 비닐기 (단, m = 0 의 경우에 한정된다), 알릴기, 프로파르길기, 페닐기, 나프틸기, 벤질기, 에톡시메틸기, 에톡시에틸기, 에톡시프로필기, 부톡시디에틸렌글리콕시에틸기, 펜타플로로에틸기, 헵타플로로프로필기, 등을 들 수 있다.R may be saturated or unsaturated may be sufficient as it, and may have an aromatic ring. Specific examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a decyl group, a stearyl group, a behenyl group, a vinyl group (however, limited to the case of m=0), an allyl group, propar a long group, a phenyl group, a naphthyl group, a benzyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, a butoxydiethyleneglycoxyethyl group, a pentafluoroethyl group, a heptafluoropropyl group, etc. are mentioned.
상기 식 (1) 로 나타내는 규소이소시아네이트 화합물의 단량체 중에서도, 하기 식 (1a) 로 나타내는 것은, 규소 산화물 피막의 전구체 등의 여러 가지 용도에서의 수요가 있고, 본 발명의 제조 방법으로 고순도의 것을 제조하는 데에 특히 적합하다.Among the monomers of the silicon isocyanate compound represented by the formula (1), those represented by the following formula (1a) are in demand in various applications such as a precursor of a silicon oxide film, and a high-purity one is produced by the production method of the present invention especially suitable for
RnSi(NCO)4-n (1a)R n Si(NCO) 4-n (1a)
본 발명의 제조 방법으로 제조되는 규소이소시아네이트 화합물의 단량체의 구체적인 화합물명으로는, 테트라이소시아나토실란, 메틸트리이소시아나토실란, 에틸트리이소시아나토실란, 디메틸디이소시아나토실란, 디에틸디이소시아나토실란, 트리메틸이소시아나토실란, 트리에틸이소시아나토실란 등을 예시할 수 있고, 이것들은, 규소 산화물 피막의 전구체 등의 여러 가지 용도에서의 수요가 있어, 고순도로 이것들을 제조할 수 있는 본 발명의 적용 대상으로서, 특히 바람직하다.Specific compound names of the monomers of the silicon isocyanate compound produced by the production method of the present invention include tetraisocyanatosilane, methyltriisocyanatosilane, ethyltriisocyanatosilane, dimethyldiisocyanatosilane, diethyldiisocyanatosilane, Trimethylisocyanatosilane, triethylisocyanatosilane, etc. can be illustrated, and these are in demand in various uses, such as a precursor of a silicon oxide film, Application of this invention which can manufacture these with high purity As the object, it is particularly preferred.
＜할로겐화규소 화합물＞<Silicon halide compound>
할로겐화규소 화합물은, 후기하는 시안산염 또는 이소시안산염과의 반응에 의해 규소이소시아네이트 화합물을 생성시키기 위한 원료이다.A silicon halide compound is a raw material for producing|generating a silicon isocyanate compound by reaction with the cyanate or isocyanate mentioned later.
「할로겐화규소 화합물」 이란, 규소와, 그 규소에 결합한 할로겐을 함유하는 화합물이다.A "silicon halide compound" is a compound containing silicon and the halogen couple|bonded with the silicon.
한정은 되지 않지만, 할로겐화규소 화합물의 전형예로는, 하기 식 (2) 로 나타내는 것을 들 수 있다.Although limitation is not carried out, What is represented by following formula (2) is mentioned as a typical example of a silicon halide compound.
Rn(OR)mSiX4-n-m (2)R n (OR) m SiX 4-nm (2)
식 (2) 에 있어서, R 은 치환되어 있어도 되는 탄화수소기이고, R 이 복수 존재하는 경우, 각각의 R 은 상이해도 된다. X 는 할로겐이다. n 및 m 은 각각 0 이상 3 이하의 정수이며, n 과 m 의 합은, 0 이상 3 이하의 정수이다.In Formula (2), R is an optionally substituted hydrocarbon group, and when two or more R exist, each R may differ. X is halogen. n and m are each an integer of 0 or more and 3 or less, and the sum of n and m is an integer of 0 or more and 3 or less.
식 (2) 에 있어서의 R 은, 포화여도 되고, 불포화여도 되고, 방향족 고리를 가지고 있어도 된다. 식 (2) 에 있어서의 R 의 구체예는, 상기한 식 (1) 에 있어서의 R 의 구체예와 동일하다.R in Formula (2) may be saturated or unsaturated may be sufficient as it, and may have an aromatic ring. The specific example of R in Formula (2) is the same as the specific example of R in said Formula (1).
식 (2) 에 있어서의 X 로는, 염소 (Cl), 브롬 (Br), 요오드 (I) 가 바람직하고, 염소 또는 브롬이 특히 바람직하다.As X in Formula (2), chlorine (Cl), bromine (Br), and iodine (I) are preferable, and chlorine or bromine is especially preferable.
식 (2) 로 나타내는 할로겐화규소 화합물은 구체적으로는, 테트라클로로실란, 메틸트리클로로실란, 에틸트리클로로실란, 디메틸디클로로실란, 디에틸디클로로실란, 트리메틸클로로실란, 트리에틸클로로실란, 테트라브로모실란, 메틸트리브로모실란, 에틸트리브로모실란, 디메틸디브로모실란, 디에틸디브로모실란, 트리메틸브로모실란, 트리에틸브로모실란 등을 예시할 수 있다.Specifically, the silicon halide compound represented by the formula (2) is tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, tetrabromosilane, Methyltribromosilane, ethyltribromosilane, dimethyldibromosilane, diethyldibromosilane, trimethylbromosilane, triethylbromosilane, etc. can be illustrated.
＜시안산염·이소시안산염＞<Cyanate/Isocyanate>
시안산염, 이소시안산염은, 상기의 할로겐화규소 화합물과의 반응에 의해 규소이소시아네이트 화합물을 생성시키기 위한 원료이다.Cyanate and isocyanate are raw materials for producing|generating a silicon isocyanate compound by reaction with said silicon halide compound.
시안산염은, M(OCN)m 으로 나타내는 (M 은 금속, m 은 자연수), 시안산 (H-O-C≡N) 과, 금속의 염이다. 본 발명의 제조 방법에 있어서의 시안산염은, 알칼리 금속 또는 알칼리 토금속과의 염인 것이 바람직하다. 알칼리 금속으로는 리튬 (Li), 나트륨 (Na), 칼륨 (K) 등이 보다 바람직하고, 알칼리 토금속으로는 마그네슘 (Mg), 칼슘 (Ca), 바륨 (Ba) 등이 보다 바람직하다.Cyanate is a salt of cyanic acid (HOC≡N) and a metal represented by M(OCN) m (M is a metal, m is a natural number). It is preferable that the cyanate in the manufacturing method of this invention is a salt with an alkali metal or alkaline-earth metal. As an alkali metal, lithium (Li), sodium (Na), potassium (K), etc. are more preferable, and magnesium (Mg), calcium (Ca), barium (Ba), etc. are more preferable as an alkaline-earth metal.
이소시안산염은, M(NCO)m 으로 나타내는 (M 은 금속, m 은 자연수), 이소시안산 (H-N=C=O) 과, 금속의 염이다. 본 발명의 제조 방법에 있어서의 이소시안산염으로는, 은 (Ag), 암모늄 등과의 염을 예시할 수 있다.The isocyanate is a salt of isocyanic acid (HN=C=O) and a metal represented by M(NCO) m (where M is a metal, m is a natural number). Salts with silver (Ag), ammonium, etc. can be illustrated as an isocyanate in the manufacturing method of this invention.
또한, 이소시안산 (H-N=C=O) 과 시안산 (H-O-C≡N) 은 호변 이성체이며, 통상적으로, 은이나 암모늄 등의 염은 이소시안산염으로서, 알칼리 금속이나 납 등의 염은 시안산염의 형태로 존재하는 것이 알려져 있다. 상당하는 규소 화합물에 대해서는, 대부분이 Si-N=C=O 의 이소시안산염의 형태를 취하는 것으로 여겨져 있다.In addition, isocyanic acid (HN=C=O) and cyanic acid (HOC≡N) are tautomers, and usually, a salt such as silver or ammonium is an isocyanate, and a salt such as an alkali metal or lead is a cyanate. It is known to exist in the form of As for the corresponding silicon compound, it is considered that most take the form of the isocyanate of Si-N=C=O.
시안산염·이소시안산염 중에서도, 입수의 용이성, 반응성, 취급의 용이함 등의 실용면으로부터, 시안산나트륨, 시안산칼륨, 시안산리튬이 특히 바람직하고, 시안산나트륨이 가장 바람직하다.Among cyanate and isocyanate, sodium cyanate, potassium cyanate, and lithium cyanate are particularly preferred, and sodium cyanate is most preferred from practical points of view such as ease of availability, reactivity, and ease of handling.
시안산염이나 이소시안산염은, 할로겐화규소 화합물 중에 함유되는 치환시키고자 하는 할로겐과 등몰 또는 그 이상 사용하는 것이 바람직하고, 시안산염이나 이소시안산염이 할로겐에 대하여 0.1 ∼ 2 당량 과잉인 것이 특히 바람직하다.The cyanate or isocyanate is preferably used in an equimolar or higher proportion to the halogen to be substituted contained in the silicon halide compound, and it is particularly preferable that the cyanate or isocyanate is in excess of 0.1 to 2 equivalents relative to the halogen. .
＜알킬렌글리콜계 화합물＞<Alkylene glycol compound>
규소이소시아네이트 화합물은, 상기한 할로겐화규소 화합물과 시안산염 또는 이소시안산염을 반응시킴으로써 얻어지는데, 반응 수율을 높이기 위해서 여러 가지 반응 촉진제를 병용하여 반응시킨다.The silicon isocyanate compound is obtained by reacting the above-described silicon halide compound with a cyanate or isocyanate, and in order to increase the reaction yield, various reaction accelerators are used in combination and reacted.
본 발명에 있어서는, 알킬렌글리콜계 화합물을 이러한 반응 촉진제로서 사용한다.In the present invention, an alkylene glycol-based compound is used as such a reaction accelerator.
본 발명의 제조 방법에 있어서의 알킬렌글리콜계 화합물로는, 에틸렌글리콜, 프로필렌글리콜, 부틸렌글리콜, 옥틸렌글리콜 등의 알킬렌글리콜류 ; 알킬렌글리콜류의 할로겐 치환체 ; 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리부틸렌글리콜 등의 폴리알킬렌글리콜류 ; 폴리알킬렌글리콜류의 할로겐 치환체 등을 들 수 있다.Examples of the alkylene glycol-based compound in the production method of the present invention include alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol and octylene glycol; halogen-substituted products of alkylene glycols; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; Halogen-substituted products of polyalkylene glycols, etc. are mentioned.
또한, 폴리알킬렌글리콜류나 그 할로겐 치환체의 에테르 유도체나 에스테르 유도체도, 본 발명의 제조 방법에 있어서의 알킬렌글리콜계 화합물의 예로서 들 수 있다.In addition, polyalkylene glycols, ether derivatives and ester derivatives of halogen-substituted products thereof are also exemplified as examples of the alkylene glycol compounds in the production method of the present invention.
에테르 유도체는, 폴리알킬렌글리콜 사슬의 편말단만이 치환기로 치환된 모노에테르 유도체여도 되고, 양말단이 치환기로 치환된 디에테르 유도체여도 된다. 에테르 유도체의 치환기로는, 메틸기, 에틸기, 프로필기, 부틸기, 올레일기, 스테아릴기, 벤질기, 페닐기 등의 탄화수소기 ; 푸르푸릴기 ; 글리세릴기 ; 소르비톨, 사카로스 등의 고리형 다가 하이드록시 화합물의 잔기 ; 등을 들 수 있다. 이들 치환기에 있어서의 수소 원자는, 할로겐으로 치환되어 있어도 된다.The ether derivative may be a monoether derivative in which only one terminal of the polyalkylene glycol chain is substituted with a substituent, or a diether derivative in which both terminals are substituted by a substituent. As a substituent of an ether derivative, Hydrocarbon groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, an oleyl group, a stearyl group, a benzyl group, and a phenyl group; furfuryl group; glyceryl group; residues of cyclic polyvalent hydroxy compounds such as sorbitol and saccharose; and the like. The hydrogen atom in these substituents may be substituted by halogen.
에스테르 유도체는, 폴리알킬렌글리콜 사슬의 편말단만이 치환기로 치환된 모노에스테르 유도체여도 되고, 양말단이 치환기로 치환된 디에스테르 유도체여도 된다. 에스테르 유도체의 치환기로는, 포르밀기, 아세틸기, 프로피오닐기, 부타노일기, 벤조일기 등을 들 수 있다. 이들 치환기에 있어서의 수소 원자는, 할로겐으로 치환되어 있어도 된다.The ester derivative may be a monoester derivative in which only one terminal of the polyalkylene glycol chain is substituted with a substituent, or a diester derivative in which both terminals are substituted by a substituent. As a substituent of the ester derivative, a formyl group, an acetyl group, a propionyl group, a butanoyl group, a benzoyl group, etc. are mentioned. The hydrogen atom in these substituents may be substituted by halogen.
폴리알킬렌글리콜 사슬의 편방의 말단이 상기한 에테르 유도체의 치환기, 다른 일방의 말단이 상기한 에스테르 유도체의 치환기로 치환된 화합물도, 본 발명의 제조 방법에 있어서의 알킬렌글리콜계 화합물로서 사용할 수 있다.Compounds in which one terminal of the polyalkylene glycol chain is substituted with the substituent of the above-described ether derivative and the other terminal of the above-described substituent of the ester derivative can also be used as the alkylene glycol-based compound in the production method of the present invention. there is.
이들 알킬렌글리콜계 화합물은, 원하는 반응성에 대응시켜 1 종 단독으로 사용해도 되고, 2 종 이상을 혼합하여 사용해도 된다.These alkylene glycol-type compounds may be used individually by 1 type corresponding to desired reactivity, and may be used in mixture of 2 or more type.
이들 알킬렌글리콜계 화합물 중에서도, 에틸렌글리콜이나 폴리에틸렌글리콜이나 그 각종 유도체는 특히 반응성이 양호하여, 본 발명에 있어서의 반응 촉진제로서 바람직하다.Among these alkylene glycol-based compounds, ethylene glycol, polyethylene glycol, and various derivatives thereof have particularly good reactivity and are preferable as a reaction accelerator in the present invention.
또한, 본 발명에서는, 공비 탈수에 의해, 반응계로부터 물을 제거함으로써, 고순도의 규소이소시아네이트 화합물의 단량체를 얻을 수 있기 때문에, 알킬렌글리콜계 화합물 중에서도, 특히 구조 내에 활성 수소를 포함하지 않는 화합물을 바람직하게 사용할 수 있다.Further, in the present invention, by removing water from the reaction system by azeotropic dehydration, a high-purity silicon isocyanate compound monomer can be obtained, so among alkylene glycol compounds, compounds that do not contain active hydrogen in their structure are particularly preferred. can be used
상기한 알킬렌글리콜계 화합물은, 계면 활성제의 정법에 따라 HLB 계산을 했을 때, 적어도 10.5 이상, 특히 13.5 이상의 HLB 를 계산 상 나타내는 구조의 화합물이, 일반적으로 양호한 결과를 부여한다.As for the above-described alkylene glycol-based compounds, when HLB is calculated according to the formula for surfactants, compounds having a structure showing an HLB of at least 10.5 or more, particularly 13.5 or more, generally give good results.
알킬렌글리콜계 화합물의 첨가량은, 할로겐화규소 화합물 100 질량부에 대하여, 0.01 질량부 이상인 것이 바람직하고, 0.05 질량부 이상인 것이 특히 바람직하다. 또한, 20 질량부 이하인 것이 바람직하고, 10 질량부 이하인 것이 특히 바람직하다.It is preferable that it is 0.01 mass part or more, and, as for the addition amount of an alkylene glycol type compound, it is especially preferable that it is 0.05 mass part or more with respect to 100 mass parts of silicon halide compounds. Moreover, it is preferable that it is 20 mass parts or less, and it is especially preferable that it is 10 mass parts or less.
상기 하한 이상이면, 반응 시간을 충분히 짧게 할 수 있어, 생산성을 향상시키기 쉽다 (0.01 질량부 미만의 첨가량에서는, 반응을 완결하는 데에 필요로 하는 시간이 5 시간 이상에 이르는 경우가 있다). 또한, 상기 상한 이하이면, 수율이 높아지기 쉽다 (예를 들어, 20 질량부를 초과하는 첨가량의 경우, 반응 속도가 커지는 반면, 알킬렌글리콜계 화합물이 OH 기를 가질 때 규소 화합물이 이것과 반응하기 때문에 수율이 저하하는 경우가 있다).If it is more than the said lower limit, reaction time can fully be shortened and it is easy to improve productivity (with the addition amount less than 0.01 mass part, the time required to complete reaction may reach 5 hours or more). In addition, if it is below the upper limit, the yield tends to be high (for example, in the case of an addition amount exceeding 20 parts by mass, the reaction rate increases, whereas when the alkylene glycol-based compound has an OH group, the silicon compound reacts with it, so the yield is may decrease).
＜용매＞<solvent>
본 발명에서는, 전술한 시안산 또는 이소시안산염과, 알킬렌글리콜계 화합물과, 후기하는 공비 용제를, 용매에 첨가하여 혼합하여, 액을 생성시킨다. 그 액은, 각 성분이 용매에 용해된 용액이어도 되고, 슬러리 등의 현탁액이어도 된다.In the present invention, the above-described cyanic acid or isocyanate, an alkylene glycol-based compound, and an azeotropic solvent described later are added to a solvent and mixed to form a liquid. A solution in which each component was dissolved in a solvent may be sufficient as the liquid, and suspensions, such as a slurry, may be sufficient as it.
공비 탈수에 의해 그 액으로부터 물을 제거한 후, 그 액에 할로겐화규소 화합물을 첨가하여 가열 반응시키는 것에 의해, 규소이소시아네이트 화합물 함유 조성물이 얻어진다.After removing water from the liquid by azeotropic dehydration, a silicon isocyanate compound containing composition is obtained by adding a silicon halide compound to the liquid and making it heat-react.
용매로는, 반응 원료, 반응 생성물을 변질시키는 경우가 없는 물질을 사용할 필요가 있다.As the solvent, it is necessary to use a substance that does not change the reaction raw material or the reaction product.
이와 같은 용매로는, 탄화수소, 할로겐화탄화수소 등의 유기 용제를 들 수 있다. 구체적으로는, n-헥산, 시클로헥산, 석유 에테르, 유동 파라핀, 벤젠, 톨루엔, 자일렌, 클로로포름, 트리클로로에틸렌, 1,1,2,2-테트라클로로에탄, 클로로벤젠, 트리에틸렌글리콜모노메틸에테르, 폴리에틸렌글리콜모노에틸에테르, 프탈산디이소노닐, 프탈산디부틸 등을 예시할 수 있다.Organic solvents, such as a hydrocarbon and halogenated hydrocarbon, are mentioned as such a solvent. Specifically, n-hexane, cyclohexane, petroleum ether, liquid paraffin, benzene, toluene, xylene, chloroform, trichloroethylene, 1,1,2,2-tetrachloroethane, chlorobenzene, triethylene glycol monomethyl Ether, polyethylene glycol monoethyl ether, diisononyl phthalate, dibutyl phthalate, etc. can be illustrated.
이들 용매는, 시안산염 또는 이소시안산염을 교반에 의해 균일하게 용해 또는 분산시키는 데에 필요한 양을 사용하는 것이 바람직하다.These solvents are preferably used in an amount necessary for uniformly dissolving or dispersing the cyanate or isocyanate by stirring.
＜공비 용제＞<azeotropic solvent>
본 발명에서는, 반응 전에, 시안산 또는 이소시안산염, 알킬렌글리콜계 화합물에 더하여, 공비 용제를 용매에 첨가한다.In the present invention, before the reaction, an azeotropic solvent is added to the solvent in addition to cyanic acid, isocyanate, and an alkylene glycol compound.
시안산 또는 이소시안산염과 할로겐화규소 화합물의 반응에 있어서, 물이 존재하면, 할로겐화규소 화합물과의 반응, 또는, 생성물인 규소이소시아네이트 화합물과 반응함으로써, 2 량체 이상의 규소이소시아네이트 화합물이 생성되기 때문에, 규소이소시아네이트 화합물 단량체의 순도의 저하, 수율의 저하로 연결된다. 물은, 이소시안산 또는 이소시안산염, 반응 촉진제 (알킬렌글리콜계 화합물), 용매에 불순물로서 함유되어 있다.In the reaction of cyanic acid or isocyanate with a silicon halide compound, when water is present, a silicon isocyanate compound of dimer or more is produced by reaction with a silicon halide compound or a product silicon isocyanate compound. It leads to a fall of the purity of an isocyanate compound monomer and a fall of a yield. Water is contained as an impurity in isocyanic acid or isocyanate, a reaction accelerator (alkylene glycol-based compound), and a solvent.
본 발명에 있어서는, 이것들에 함유되는 물을 제거하기 위해서, 공비 용제를 용매에 첨가하여, 공비 탈수를 실시한다.In this invention, in order to remove the water contained in these, an azeotropic solvent is added to a solvent, and azeotropic dehydration is performed.
본 발명에서는, 특허문헌 2 와 같이, 원료인 시안산염이나 이소시안산염을 미리 탈수하는 방법과 비교하여, 물을 충분히 제거할 수 있기 때문에, 규소이소시아네이트 화합물 단량체의 순도가 높은 규소이소시아네이트 화합물 함유 조성물을 얻을 수 있다.In the present invention, as in Patent Document 2, compared with the method of dehydrating the cyanate or isocyanate as a raw material in advance, since water can be sufficiently removed, a silicon isocyanate compound-containing composition with a high purity of the silicon isocyanate compound monomer can be obtained
공비 용제로는, 반응 원료, 반응 생성물을 변질시키는 경우가 없는 용제를 사용할 필요가 있다. 공비 용제로서, 예를 들어, 화학 구조 중에 활성 수소를 포함하지 않는 유기 용제를 들 수 있다.As the azeotropic solvent, it is necessary to use a solvent that does not alter the reaction raw material or the reaction product. As an azeotropic solvent, the organic solvent which does not contain active hydrogen in a chemical structure is mentioned, for example.
이러한 공비 용제로는, 탄화수소가 바람직하고, 방향족 탄화수소가 특히 바람직하다. 구체적인 화합물로는, 벤젠, 톨루엔, 자일렌, 에틸벤젠 등을 예시할 수 있다.As such an azeotropic solvent, a hydrocarbon is preferable, and an aromatic hydrocarbon is especially preferable. Specific examples of the compound include benzene, toluene, xylene, and ethylbenzene.
공비 용제는, 1 종 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다.An azeotropic solvent may be used individually by 1 type, and may use 2 or more types together.
본 발명의 규소이소시아네이트 화합물 함유 조성물의 제조 방법은, 이하에 서술하는 공정 (A) 내지 공정 (D) 까지를 갖는다.The method for producing the silicon isocyanate compound-containing composition of the present invention includes steps (A) to (D) described below.
[공정 (A)][Process (A)]
공정 (A) 에서는, 각각 상기한, 시안산염 또는 이소시안산, 공비 용제, 알킬렌글리콜계 화합물, 용매를 혼합시켜 액을 생성시킨다. 그 액은, 각 성분이 용매에 용해된 용액이어도 되고, 슬러리 등의 현탁액이어도 된다.In the step (A), the above-described cyanate or isocyanic acid, an azeotropic solvent, an alkylene glycol-based compound, and a solvent are mixed to form a liquid. A solution in which each component was dissolved in a solvent may be sufficient as the liquid, and suspensions, such as a slurry, may be sufficient as it.
공정 (A) 에 있어서, 각 성분의 투입의 순서에 특별히 한정은 없다. 각 성분이 충분히 혼합되도록, 반응 용기 내를 교반하면서 공정 (A) 를 실시하는 것이 바람직하다.In a process (A), there is no limitation in particular in the order of injection|throwing-in of each component. It is preferable to perform a process (A), stirring the inside of a reaction container so that each component may be fully mixed.
[공정 (B)][Process (B)]
공정 (B) 에서는, 공정 (A) 에서 생성시킨 액을 가열하여, 물과 공비 용제를 제거한다. 공정 (B) 를 실시함으로써, 액으로부터 물이 제거되고, 그 결과, 시안산염 또는 이소시안산과 할로겐화규소 화합물의 반응시에, 물과의 반응에 의한 다량화 반응을 방지할 수 있고, 규소이소시아네이트 화합물 단량체의 순도가 높은 규소이소시아네이트 화합물 함유 조성물을 얻을 수 있다.In the step (B), the liquid produced in the step (A) is heated to remove water and the azeotropic solvent. By performing the step (B), water is removed from the liquid, and as a result, at the time of reaction of cyanate or isocyanic acid with a silicon halide compound, the multimerization reaction by reaction with water can be prevented, and silicon isocyanate A composition containing a silicon isocyanate compound having a high purity of the compound monomer can be obtained.
공정 (B) 에서, 공비 탈수를 실시할 때의 조건에 대하여 특별히 한정은 없지만, 상압하에 있어서 공비 탈수를 실시한 후에, 감압하여 추가로 공비 탈수를 실시하는 것이 바람직하다.In the step (B), the conditions for azeotropic dehydration are not particularly limited, but after azeotropic dehydration is carried out under normal pressure, it is preferable to further perform azeotropic dehydration under reduced pressure.
상압하에서의 공비 탈수에 있어서의 액 온도는, 20 ℃ 이상인 것이 바람직하고, 50 ℃ 이상인 것이 보다 바람직하고, 100 ℃ 이상인 것이 특히 바람직하다. 또한, 250 ℃ 이하인 것이 바람직하고, 230 ℃ 이하인 것이 보다 바람직하고, 200 ℃ 이하인 것이 특히 바람직하다.It is preferable that it is 20 degreeC or more, and, as for the liquid temperature in azeotropic dehydration under normal pressure, it is more preferable that it is 50 degreeC or more, It is especially preferable that it is 100 degreeC or more. Moreover, it is preferable that it is 250 degrees C or less, It is more preferable that it is 230 degrees C or less, It is especially preferable that it is 200 degrees C or less.
액 온도가 상기 범위이면, 규소이소시아네이트 화합물 단량체의 순도, 수율을 저하시키지 않고 규소이소시아네이트 화합물 함유 조성물을 제조하는 것이 가능하다.If the liquid temperature is within the above range, it is possible to produce a silicon isocyanate compound-containing composition without reducing the purity and yield of the silicon isocyanate compound monomer.
또한, 상압하에서 공비 탈수를 실시한 후에 감압하여 추가로 공비 탈수를 실시할 때의 액 온도는, 20 ℃ 이상인 것이 바람직하고, 50 ℃ 이상인 것이 보다 바람직하고, 100 ℃ 이상인 것이 특히 바람직하다. 또한, 250 ℃ 이하인 것이 바람직하고, 230 ℃ 이하인 것이 보다 바람직하고, 200 ℃ 이하인 것이 특히 바람직하다.In addition, after azeotropic dehydration under normal pressure, the liquid temperature for further azeotropic dehydration under reduced pressure is preferably 20°C or higher, more preferably 50°C or higher, and particularly preferably 100°C or higher. Moreover, it is preferable that it is 250 degrees C or less, It is more preferable that it is 230 degrees C or less, It is especially preferable that it is 200 degrees C or less.
감압도 (압력) 는, 0.1 ㎪ 이상인 것이 바람직하고, 0.3 ㎪ 이상인 것이 보다 바람직하고, 0.5 ㎪ 이상인 것이 특히 바람직하다. 또한, 101.3 ㎪ 이하인 것이 바람직하고, 90 ㎪ 이하인 것이 보다 바람직하고, 50 ㎪ 이하인 것이 특히 바람직하다.It is preferable that pressure reduction degree (pressure) is 0.1 kPa or more, It is more preferable that it is 0.3 kPa or more, It is especially preferable that it is 0.5 kPa or more. Moreover, it is preferable that it is 101.3 kPa or less, It is more preferable that it is 90 kPa or less, It is especially preferable that it is 50 kPa or less.
액 온도, 감압도 (압력) 가 상기 범위이면, 규소이소시아네이트 화합물 단량체의 순도, 수율을 저하시키지 않고 규소이소시아네이트 화합물 함유 조성물을 제조하는 것이 가능하다.When the liquid temperature and the degree of reduced pressure (pressure) are within the above ranges, it is possible to produce a silicon isocyanate compound-containing composition without reducing the purity and yield of the silicon isocyanate compound monomer.
[공정 (C)][Process (C)]
공정 (C) 에서는, 공정 (B) 에서 물과 공비 용제를 제거한 액에, 상기한 할로겐화규소 화합물을 첨가하고, 시안산 또는 이소시안산염과의 반응에 의해, 규소이소시아네이트 화합물을 생성시킨다.In the step (C), the above-described silicon halide compound is added to the liquid from which water and the azeotropic solvent are removed in the step (B), and a silicon isocyanate compound is produced by reaction with cyanic acid or isocyanate.
공정 (C) 에 있어서의 반응 온도는 실온 이하에서 실시할 수도 있지만, 실온이면 5 시간 내지 그 이상의 장시간을 필요로 하는 경우가 많다. 한편, 200 ℃ 보다 높은 온도에서는, 반응 시간은 짧기는 하지만, 생성물인 규소이소시아네이트 화합물이 부반응을 일으키는 경우가 있다.Although the reaction temperature in a process (C) can also be carried out at room temperature or less, if it is room temperature, it requires a long time of 5 hours or more in many cases. On the other hand, at a temperature higher than 200°C, although the reaction time is short, the silicon isocyanate compound as a product may cause a side reaction.
이 때문에, 반응 온도는, 실온 이상인 것이 바람직하고, 50 ℃ 이상인 것이 보다 바람직하고, 100 ℃ 이상인 것이 특히 바람직하다. 또한, 200 ℃ 이하인 것이 바람직하고, 190 ℃ 이하인 것이 보다 바람직하고, 180 ℃ 이하인 것이 특히 바람직하다.For this reason, it is preferable that reaction temperature is room temperature or more, It is more preferable that it is 50 degreeC or more, It is especially preferable that it is 100 degreeC or more. Moreover, it is preferable that it is 200 degrees C or less, It is more preferable that it is 190 degrees C or less, It is especially preferable that it is 180 degrees C or less.
상기 하한 이상이면, 단시간에 (최대 2 시간 정도로) 반응을 종료시킬 수 있다. 또한, 상기 상한 이하이면, 규소이소시아네이트 화합물의 부반응을 억제하기 쉽다.If it is more than the said lower limit, reaction can be terminated in a short time (about 2 hours at most). Moreover, it is easy to suppress the side reaction of a silicon isocyanate compound as it is below the said upper limit.
[공정 (D)][Process (D)]
공정 (D) 에서는, 공정 (C) 에 있어서의 반응으로 발생한 규소이소시아네이트 화합물을 함유하는 액을 가열하여 그 규소이소시아네이트 화합물을 유거하여 회수한다.At the step (D), the liquid containing the silicon isocyanate compound generated by the reaction in the step (C) is heated, and the silicon isocyanate compound is distilled off and recovered.
공정 (D) 에 있어서는, 상압하에서 액을 가열하여 규소이소시아네이트 화합물을 유거해도 되고, 감압 상태에서 유거해도 된다. 처음에는 상압하에서 유거하고, 추가로, 감압 상태에서 유거해도 되고, 그와 같이 하면, 수율이 향상되기 쉽다.In the step (D), the silicon isocyanate compound may be distilled off by heating the liquid under normal pressure, or may be distilled off under reduced pressure. At first, it distills out under normal pressure, and further, you may distill in a pressure-reduced state, and when it does so, a yield tends to improve.
규소이소시아네이트 화합물의 상압하에서의 유거에 있어서의 액 온도는, 100 ℃ 이상인 것이 바람직하고, 120 ℃ 이상인 것이 보다 바람직하고, 150 ℃ 이상인 것이 특히 바람직하다. 또한, 250 ℃ 이하인 것이 바람직하고, 200 ℃ 이하인 것이 보다 바람직하고, 190 ℃ 이하인 것이 특히 바람직하다.It is preferable that it is 100 degreeC or more, as for the liquid temperature in distillation under normal pressure of a silicon isocyanate compound, it is more preferable that it is 120 degreeC or more, It is especially preferable that it is 150 degreeC or more. Moreover, it is preferable that it is 250 degrees C or less, It is more preferable that it is 200 degrees C or less, It is especially preferable that it is 190 degrees C or less.
액 온도가 상기 범위이면, 규소이소시아네이트 화합물 단량체의 순도, 수율을 저하시키지 않고 규소이소시아네이트 화합물 함유 조성물을 제조하는 것이 가능하다.If the liquid temperature is within the above range, it is possible to produce a silicon isocyanate compound-containing composition without reducing the purity and yield of the silicon isocyanate compound monomer.
또한, 상압하에서 유거한 후에 추가로 감압을 실시하여 유거하는 경우의 액 온도는, 100 ℃ 이상인 것이 바람직하고, 120 ℃ 이상인 것이 보다 바람직하고, 150 ℃ 이상인 것이 특히 바람직하다. 또한, 250 ℃ 이하인 것이 바람직하고, 200 ℃ 이하인 것이 보다 바람직하고, 190 ℃ 이하인 것이 특히 바람직하다.Moreover, it is preferable that it is 100 degreeC or more, and, as for the liquid temperature in the case of carrying out further pressure reduction and distilling off after distilling under normal pressure, it is more preferable that it is 120 degreeC or more, It is especially preferable that it is 150 degreeC or more. Moreover, it is preferable that it is 250 degrees C or less, It is more preferable that it is 200 degrees C or less, It is especially preferable that it is 190 degrees C or less.
감압도 (압력) 는, 0.1 ㎪ 이상인 것이 바람직하고, 0.3 ㎪ 이상인 것이 보다 바람직하고, 0.5 ㎪ 이상인 것이 특히 바람직하다. 또한, 101.3 ㎪ 이하인 것이 바람직하고, 90 ㎪ 이하인 것이 보다 바람직하고, 80 ㎪ 이하인 것이 특히 바람직하다.It is preferable that pressure reduction degree (pressure) is 0.1 kPa or more, It is more preferable that it is 0.3 kPa or more, It is especially preferable that it is 0.5 kPa or more. Moreover, it is preferable that it is 101.3 kPa or less, It is more preferable that it is 90 kPa or less, It is especially preferable that it is 80 kPa or less.
액 온도, 감압도 (압력) 가 상기 범위이면, 규소이소시아네이트 화합물 단량체의 순도, 수율을 저하시키지 않고 규소이소시아네이트 화합물 함유 조성물을 제조하는 것이 가능하다.When the liquid temperature and the degree of reduced pressure (pressure) are within the above ranges, it is possible to produce a silicon isocyanate compound-containing composition without reducing the purity and yield of the silicon isocyanate compound monomer.
본 발명에서는, 공정 (C) 에 있어서의 할로겐화규소 화합물과 시안산 또는 이소시안산염의 반응 전에, 공정 (B) 에 있어서, 공비 탈수에 의해 액으로부터 물을 제거하고 있다. 이 때문에, 공정 (C) 에서 생성되는 규소이소시아네이트 화합물에는, 바람직하지 않은 부반응 생성물인 2 량체 이상의 화합물의 함유량이 매우 적고, 단량체가 많이 포함되어 있다.In the present invention, before the reaction of the silicon halide compound with cyanic acid or isocyanate in the step (C), in the step (B), water is removed from the liquid by azeotropic dehydration. For this reason, there is very little content of the compound more than dimer which is an undesirable side reaction product in the silicon isocyanate compound produced|generated at the process (C), and contains many monomers.
따라서, 공정 (D) 에 있어서 규소이소시아네이트 화합물을 유거함으로써 회수한 조성물 (규소이소시아네이트 화합물 함유 조성물) 에는, 규소이소시아네이트 화합물 단량체가, 많이 포함되어 있다.Therefore, many silicon isocyanate compound monomers are contained in the composition (silicon isocyanate compound containing composition) collect|recovered by distilling off a silicon isocyanate compound in a process (D).
구체적으로는, 공정 (D) 에서 회수된 규소이소시아네이트 화합물 함유 조성물은, 통상적으로, 규소이소시아네이트 화합물 단량체를 80 질량％ 이상 함유한다 (규소이소시아네이트 화합물 단량체의 순도가 80 질량％ 이상이다). 또한, 본 발명의 방법에 의하면, 공정 (D) 에서 회수된 단계에서, 규소이소시아네이트 화합물 단량체를 85 질량％ 이상 함유하는 규소이소시아네이트 화합물 함유 조성물이나, 규소이소시아네이트 화합물 단량체를 90 질량％ 이상 함유하는 규소이소시아네이트 화합물 함유 조성물을 얻는 것도 가능하다.Specifically, the silicon isocyanate compound-containing composition recovered in the step (D) contains usually 80 mass% or more of the silicon isocyanate compound monomer (the purity of the silicon isocyanate compound monomer is 80 mass% or more). Further, according to the method of the present invention, in the step recovered in the step (D), a composition containing a silicon isocyanate compound containing 85 mass% or more of a silicon isocyanate compound monomer, or a silicon isocyanate containing 90 mass% or more of a silicon isocyanate compound monomer It is also possible to obtain a compound containing composition.
또한, 본 명세서에 있어서의 규소이소시아네이트 화합물 단량체의 순도는, 수소 불꽃 이온화형 검출기를 사용한 가스 크로마토그래피로 측정하고, 그 면적비로부터 산출된 수치이다.In addition, the purity of the silicon isocyanate compound monomer in this specification is the numerical value computed from the area ratio measured by the gas chromatography using the hydrogen flame ionization type detector.
[증류 공정 (정제 공정)][Distillation process (refining process)]
상기와 같이, 본 발명의 방법에서는, 공정 (D) 에서 회수된 단계에서, 규소이소시아네이트 화합물 단량체의 순도가 80 질량％ 이상인 규소이소시아네이트 화합물 함유 조성물을 얻을 수 있다.As described above, in the method of the present invention, in the step recovered in the step (D), a silicon isocyanate compound-containing composition in which the purity of the silicon isocyanate compound monomer is 80% by mass or more can be obtained.
공정 (D) 에서 회수된 규소이소시아네이트 화합물 함유 조성물을, 추가로, 상압 및/또는 감압하에서 가열하여 증류함으로써, 규소이소시아네이트 화합물 단량체의 순도를 더욱 높일 (고순도화할) 수 있다.By further heating and distilling the silicon isocyanate compound-containing composition recovered in the step (D) under normal pressure and/or reduced pressure, the purity of the silicon isocyanate compound monomer can be further increased (higher purity).
증류에는, 공지된 방법을 사용할 수 있고, 예를 들어, 정류탑을 사용한 방법을 들 수 있다.A well-known method can be used for distillation, For example, the method using a rectification column is mentioned.
본 발명의 방법에서는, 공정 (D) 에서 회수된 단계에 있어서 이미, 규소이소시아네이트 화합물 함유 조성물 중의 규소이소시아네이트 화합물 단량체의 순도가, 종래의 방법으로 얻어진 것 보다 높기 때문에, 증류 공정을 거친 규소이소시아네이트 화합물 함유 조성물 중의 규소이소시아네이트 화합물 단량체의 순도도 높다.In the method of the present invention, since the purity of the silicon isocyanate compound monomer in the silicon isocyanate compound-containing composition is higher than that obtained by the conventional method in the step recovered in the step (D), the silicon isocyanate compound that has been subjected to the distillation step contains The purity of the silicon isocyanate compound monomer in the composition is also high.
구체적으로는, 증류 공정 (정제 공정) 을 거친 후의 규소이소시아네이트 화합물 함유 조성물 중의 규소이소시아네이트 화합물 단량체의 순도는, 90 질량％ 이상인 것이 바람직하고, 95 질량％ 이상인 것이 보다 바람직하고, 98 질량％ 이상인 것이 특히 바람직하고, 99.1 질량％ 이상인 것이 더욱 바람직하고, 99.5 질량％ 이상인 것이 가장 바람직하다.Specifically, the purity of the silicon isocyanate compound monomer in the silicon isocyanate compound-containing composition after the distillation step (refining step) is preferably 90 mass% or more, more preferably 95 mass% or more, and particularly 98 mass% or more Preferably, it is more preferable that it is 99.1 mass % or more, and it is most preferable that it is 99.5 mass % or more.
본 발명은, 상기한 규소이소시아네이트 화합물 함유 조성물의 제조 방법으로 제조한 규소이소시아네이트 화합물 함유 조성물을 규소 전구체로서 사용하는 것을 특징으로 하는 규소 산화물 또는 규소 산화물 피막의 제조 방법에 관한 것이기도 하다.The present invention also relates to a method for producing a silicon oxide or silicon oxide film, wherein the composition containing a silicon isocyanate compound prepared by the method for producing a composition containing a silicon isocyanate compound described above is used as a silicon precursor.
본 발명의 규소이소시아네이트 화합물 함유 조성물의 제조 방법으로 제조한 규소이소시아네이트 화합물 함유 조성물이나, 이러한 규소이소시아네이트 화합물 함유 조성물을 정제한 규소이소시아네이트 화합물 함유 조성물은, 규소이소시아네이트 화합물 단량체의 순도가 높기 때문에, 규소 산화물 또는 규소 산화물 피막을 제조하기 위한 규소 전구체로서 적합하다.The silicon isocyanate compound-containing composition produced by the method for producing the silicon isocyanate compound-containing composition of the present invention, or the silicon isocyanate compound-containing composition obtained by refining such a silicon isocyanate compound-containing composition, since the purity of the silicon isocyanate compound monomer is high, silicon oxide or It is suitable as a silicon precursor for producing a silicon oxide film.
실시예Example
이하에, 실시예를 들어 본 발명을 더욱 구체적으로 설명하지만, 본 발명은, 그 요지를 벗어나지 않는 한 이들 실시예로 한정되는 것은 아니다.Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples unless it departs from the summary.
제조예 1Preparation Example 1
시안산나트륨 (쥰세이 화학 주식회사 제조) 26.0 질량부 (0.4 몰부), 폴리옥시에틸렌알킬에테르 0.4 질량부, 유동 파라핀 (신니혼 석유 주식회사 제조, 상품명 : 하이 화이트 350) 23.8 질량부를, 톨루엔 17.9 질량부에 혼합한 후, 상압하, 액체 온도 110 ∼ 200 ℃ 의 조건으로 톨루엔과 물의 공비 탈수를 실시하였다. 그 후, 액체 온도 200 ℃, 감압도를 3 ㎪ 의 조건으로 추가로 공비 탈수를 실시하였다.Sodium cyanate (manufactured by Junsei Chemical Co., Ltd.) 26.0 parts by mass (0.4 mol parts), 0.4 parts by mass of polyoxyethylene alkyl ether, 23.8 parts by mass of liquid paraffin (manufactured by Shin-Nippon Petroleum Corporation, trade name: Hi White 350), 17.9 parts by mass of toluene After mixing, azeotropic dehydration of toluene and water was performed under normal pressure and liquid temperature of 110-200 degreeC. Thereafter, azeotropic dehydration was further performed under conditions of a liquid temperature of 200°C and a degree of reduced pressure of 3 kPa.
공비 탈수 후, 메틸트리클로로실란 (도쿄 화성 공업 주식회사 제조) 14.9 질량부 (0.1 몰부) 를 적하하고, 170 ℃ 에서 1 시간 반응시킨 후, 상압하에서 액체 온도 150 ∼ 190 ℃ 의 범위에서 액체를 유출시켜, 순도 80 질량％ 의 메틸트리이소시아나토실란을 함유하는 조성물을 13.5 질량부 얻었다.After azeotropic dehydration, 14.9 parts by mass (0.1 mol parts) of methyltrichlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) is added dropwise, reacted at 170° C. for 1 hour, and then the liquid is drained at a liquid temperature of 150 to 190° C. under normal pressure. and 13.5 mass parts of compositions containing 80 mass % of purity methyltriisocyanatosilane were obtained.
또한, 얻어진 조성물 10.0 질량부를 상압하에서 액체 온도 150 ∼ 190 ℃ 의 범위에서 증류하여, 순도 99 ％ 를 초과하는 메틸트리이소시아나토실란을 함유하는 조성물을 5.0 질량부 얻었다.Furthermore, 10.0 mass parts of obtained compositions were distilled under normal pressure in the range of 150-190 degreeC of liquid temperatures, and 5.0 mass parts of compositions containing the methyltriisocyanatosilane exceeding 99% of purity were obtained.
제조예 2Preparation 2
시안산나트륨 (쥰세이 화학 주식회사 제조) 39.8 질량부 (0.6 몰부), 폴리옥시에틸렌알킬에테르 0.3 질량부, 유동 파라핀 (신니혼 석유 주식회사 제조, 상품명 : 하이 화이트 350) 26.3 질량부를, 에틸벤젠 26.3 질량부에 혼합한 후, 상압하, 액체 온도 110 ∼ 200 ℃ 의 조건으로 에틸벤젠과 물의 공비 탈수를 실시하였다. 그 후, 액체 온도 200 ℃, 감압도를 3 ㎪ 의 조건으로 추가로 공비 탈수를 실시하였다.Sodium cyanate (manufactured by Junsei Chemical Co., Ltd.) 39.8 parts by mass (0.6 mol parts), 0.3 parts by mass of polyoxyethylene alkyl ether, 26.3 parts by mass of liquid paraffin (manufactured by Shin-Nippon Petroleum Corporation, trade name: Hi White 350), 26.3 parts by mass of ethylbenzene After mixing with ethylbenzene, azeotropic dehydration of ethylbenzene and water was performed under normal pressure and the liquid temperature of 110-200 degreeC. Thereafter, azeotropic dehydration was further performed under conditions of a liquid temperature of 200°C and a degree of reduced pressure of 3 kPa.
공비 탈수 후, 테트라클로로실란 (도쿄 화성 공업 주식회사 제조) 17.0 부 (0.1 몰부) 를 적하하고, 170 ℃ 에서 1 시간 반응시킨 후, 액체 온도 160 ∼ 180 ℃, 감압도 60 ∼ 80 ㎪ 의 범위에서 액체를 유출시켜, 순도 80 질량％ 의 테트라이소시아나토실란을 함유하는 조성물을 13.7 질량부 얻었다.After azeotropic dehydration, 17.0 parts (0.1 mol parts) of tetrachlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) is added dropwise and reacted at 170° C. for 1 hour, followed by a liquid temperature of 160 to 180° C. and a reduced pressure of 60 to 80 kPa. was distilled to obtain 13.7 parts by mass of a composition containing tetraisocyanatosilane having a purity of 80% by mass.
또한, 얻어진 조성물 10.0 질량부를 상압하에서 액체 온도 150 ∼ 190 ℃ 의 범위에서 증류하여, 순도 99 ％ 를 초과하는 테트라이소시아나토실란을 함유하는 조성물을 5.0 질량부 얻었다.Furthermore, 10.0 mass parts of obtained compositions were distilled in the range of 150-190 degreeC liquid temperature under normal pressure, and 5.0 mass parts of compositions containing the tetraisocyanatosilane exceeding 99% of purity were obtained.
제조예 3Preparation 3
시안산나트륨 (쥰세이 화학 주식회사 제조) 26.0 질량부 (0.4 몰부), 폴리옥시에틸렌알킬에테르 0.4 질량부, 유동 파라핀 (신니혼 석유 주식회사 제조, 상품명 : 하이 화이트 350) 23.8 질량부에 메틸트리클로로실란 (도쿄 화성 공업 주식회사 제조) 14.9 질량부 (0.1 몰부) 를 적하하고, 170 ℃ 에서 1 시간 반응시킨 후, 상압하에서 액체 온도 150 ∼ 190 ℃ 의 범위에서 액체를 유출시킨 결과, 순도 70 질량％ 의 메틸트리이소시아나토실란을 함유하는 조성물을 13.0 질량부 얻었다.Sodium cyanate (manufactured by Junsei Chemical Co., Ltd.) 26.0 parts by mass (0.4 mol parts), 0.4 parts by mass of polyoxyethylene alkyl ether, liquid paraffin (manufactured by Shin-Nippon Petroleum Co., Ltd., trade name: Hi White 350) 23.8 parts by mass of methyltrichlorosilane ( After 14.9 mass parts (0.1 mol part) of Tokyo Chemical Industry Co., Ltd. product) were dripped and made to react at 170 degreeC for 1 hour, as a result of distilling a liquid in the range of 150-190 degreeC of liquid temperature under normal pressure, methyltriy of 70 mass % purity 13.0 mass parts of compositions containing socyanatosilane were obtained.
또한, 얻어진 조성물 10.0 질량부를 실시예 1 과 동일한 조건으로 증류시킨 결과, 순도 90 질량％ 의 메틸트리이소시아나토실란을 함유하는 조성물을 5.0 질량부 얻었다.Moreover, when 10.0 mass parts of obtained compositions were distilled on the conditions similar to Example 1, 5.0 mass parts of compositions containing 90 mass % purity methyltriisocyanatosilane were obtained.
제조예 4Preparation 4
시안산나트륨 (쥰세이 화학 주식회사 제조) 26.0 질량부 (0.4 몰부), 폴리옥시에틸렌알킬에테르 0.4 질량부, 유동 파라핀 (신니혼 석유 주식회사 제조 상품명 : 하이 화이트 350) 23.8 질량부에, 몰레큘러 시브스 10.0 질량부를 혼합하여 24 시간 정치하였다.Sodium cyanate (manufactured by Junsei Chemical Co., Ltd.) 26.0 parts by mass (0.4 mol parts), 0.4 parts by mass of polyoxyethylene alkyl ether, liquid paraffin (New Nippon Petroleum Co., Ltd. trade name: High White 350) 23.8 parts by mass, Molecular Sieves 10.0 A mass part was mixed and it left still for 24 hours.
그 후, 몰레큘러 시브스의 제거를 시도했지만, 슬러리상이고, 시안산나트륨과 혼합 상태였기 때문에 분리할 수 없어 탈수할 수 없었다.After that, the removal of the molecular sieves was attempted, but since it was in the form of a slurry and was in a mixed state with sodium cyanate, it could not be separated and could not be dehydrated.
산업상 이용가능성Industrial Applicability
본 발명에 있어서의 규소이소시아네이트 화합물 함유 조성물은, Si-NCO 결합을 갖는 규소이소시아네이트 화합물을 함유하고 있고, 예를 들어 알코올이나 제 1 아민, 제 2 아민, 카르복실산 등의 활성 수소를 분자 중에 포함하는 화합물과 용이하게 반응하기 때문에, 폴리머의 개질제로서, 혹은 중합물의 성분으로서 용이하게 도입할 수 있고, 규소의 특성을 공업 재료에 부가할 수 있다. 또한, 물과 신속하게 반응하는 것으로부터, 공기 중의 수분 또는, 유리, 세라믹스, 금속 등의 표면에 존재하는 흡착수 등과 반응하여, 밀착성이 높은 산화규소막을 형성시킬 수 있다.The silicon isocyanate compound-containing composition in the present invention contains a silicon isocyanate compound having a Si-NCO bond, and contains active hydrogen such as alcohol, primary amine, secondary amine, and carboxylic acid in the molecule. Since it reacts easily with the compound used in the present invention, it can be easily introduced as a polymer modifier or as a component of a polymer, and the properties of silicon can be added to industrial materials. In addition, since it reacts rapidly with water, it reacts with moisture in the air or adsorbed water existing on the surface of glass, ceramics, metal, or the like to form a silicon oxide film with high adhesion.
Claims (7)
(A) 그 시안산염 또는 이소시안산염과, 공비 용제와, 그 알킬렌글리콜계 화합물과, 그 용매를 혼합시켜 액을 생성시키는 공정
(B) 그 액을 가열하여, 물과 그 공비 용제를 제거하는 공정
(C) 그 액에 그 할로겐화규소 화합물을 첨가하여 그 규소이소시아네이트 화합물을 생성시키는 공정
(D) 그 액을 가열하여 그 규소이소시아네이트 화합물을 유거하여 회수하는 공정A method for producing a silicon isocyanate compound-containing composition in which a silicon isocyanate compound is produced by reacting a silicon halide compound with a cyanate or isocyanate in the presence of a solvent and an alkylene glycol compound, from the following steps (A) to (D) A method for producing a composition containing a silicon isocyanate compound, characterized in that it has a.
(A) step of mixing the cyanate or isocyanate, the azeotropic solvent, the alkylene glycol compound, and the solvent to produce a liquid
(B) a step of heating the liquid to remove water and its azeotropic solvent
(C) A step of adding the silicon halide compound to the solution to produce the silicon isocyanate compound
(D) a step of heating the liquid to distill off and recover the silicon isocyanate compound
상기 공비 용제가 화학 구조 중에 활성 수소를 포함하지 않는 용제인, 규소이소시아네이트 화합물 함유 조성물의 제조 방법.The method of claim 1,
The method for producing a composition containing a silicon isocyanate compound, wherein the azeotropic solvent is a solvent that does not contain active hydrogen in its chemical structure.
상기 공비 용제가 방향족 탄화수소인, 규소이소시아네이트 화합물 함유 조성물의 제조 방법.The method of claim 1,
The method for producing a composition containing a silicon isocyanate compound, wherein the azeotropic solvent is an aromatic hydrocarbon.
상기 공비 용제가 톨루엔, 자일렌 및 에틸벤젠으로 이루어지는 군에서 선택되는 1 종 이상의 용제인, 규소이소시아네이트 화합물 함유 조성물의 제조 방법.The method of claim 1,
The method for producing a composition containing a silicon isocyanate compound, wherein the azeotropic solvent is at least one solvent selected from the group consisting of toluene, xylene and ethylbenzene.
제조되는 규소이소시아네이트 화합물 함유 조성물이, 규소이소시아네이트 화합물의 단량체를 80 질량％ 이상 함유하는 것인, 규소이소시아네이트 화합물 함유 조성물의 제조 방법.5. The method according to any one of claims 1 to 4,
The method for producing a composition containing a silicon isocyanate compound, wherein the composition containing a silicon isocyanate compound to be produced contains 80% by mass or more of the monomer of the silicon isocyanate compound.
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| JPJP-P-2019-139392 | 2019-07-30 | ||
| JP2019139392 | 2019-07-30 | ||
| PCT/JP2020/028634 WO2021020325A1 (en) | 2019-07-30 | 2020-07-27 | Silicon isocyanate compound-containing composition and production method therefor |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54119419A (en) | 1978-03-09 | 1979-09-17 | Toshiba Silicone | Manufacture of organoisocyanate silane |
| JPS55102589A (en) | 1980-01-26 | 1980-08-05 | Toyama Chem Co Ltd | Preparation of organo-silicon isocyanates |
| JPS5626895A (en) | 1979-08-09 | 1981-03-16 | Ichiro Kijima | Preparation of silicon isocyanate compound |
| JPS62167785A (en) | 1987-01-08 | 1987-07-24 | Matsumoto Seiyaku Kogyo Kk | Production of silicon isocyanate |
| JPH07188257A (en) | 1993-03-10 | 1995-07-25 | Yoshisaki Abe | Production of triisocynatosilane |
| JP2000247982A (en) | 1999-02-26 | 2000-09-12 | Matsumoto Seiyaku Kogyo Kk | Production of isocyanatodisiloxane |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835515B2 (en) * | 1977-09-12 | 1983-08-03 | 日本化成株式会社 | Production method of isocyanuric acid ester |
| JPS5832887A (en) * | 1981-08-19 | 1983-02-25 | Matsumoto Seiyaku Kogyo Kk | Production of silicon isocyanate |
| JP3522902B2 (en) * | 1995-06-03 | 2004-04-26 | 信越化学工業株式会社 | Method for producing ureido group-containing alkoxysilane |
| JP2001240796A (en) * | 2000-02-29 | 2001-09-04 | Ube Nitto Kasei Co Ltd | Organic/inorganic hybrid-inorganic composite gradient material and its use |
| DE60231220D1 (en) * | 2001-09-21 | 2009-04-02 | Dow Corning Toray Co Ltd | PROCESS FOR THE PREPARATION OF THIOCYANATE-COOKED ORGANOALKOXYSILANES |
| JP4310639B2 (en) * | 2004-04-30 | 2009-08-12 | 信越化学工業株式会社 | Process for producing organosilicon compound containing β-ketoester structure |
| EP2328619B1 (en) * | 2008-08-22 | 2016-12-07 | Baxalta GmbH | Polymeric benzyl carbonate-derivatives |
| JP6243215B2 (en) * | 2013-12-18 | 2017-12-06 | 大陽日酸株式会社 | Method for purifying and supplying triisocyanatosilane |
| US10266554B2 (en) * | 2017-05-31 | 2019-04-23 | Momentive Performance Materials Inc. | Preparation of isocyanatosilanes |
-
2020
- 2020-07-27 WO PCT/JP2020/028634 patent/WO2021020325A1/en active Application Filing
- 2020-07-27 KR KR1020227003738A patent/KR20220039729A/en unknown
- 2020-07-27 JP JP2021537013A patent/JPWO2021020325A1/ja active Pending
- 2020-07-27 CN CN202080052675.4A patent/CN114174307A/en active Pending
- 2020-07-28 TW TW109125430A patent/TW202112789A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54119419A (en) | 1978-03-09 | 1979-09-17 | Toshiba Silicone | Manufacture of organoisocyanate silane |
| JPS5626895A (en) | 1979-08-09 | 1981-03-16 | Ichiro Kijima | Preparation of silicon isocyanate compound |
| JPS55102589A (en) | 1980-01-26 | 1980-08-05 | Toyama Chem Co Ltd | Preparation of organo-silicon isocyanates |
| JPS62167785A (en) | 1987-01-08 | 1987-07-24 | Matsumoto Seiyaku Kogyo Kk | Production of silicon isocyanate |
| JPH07188257A (en) | 1993-03-10 | 1995-07-25 | Yoshisaki Abe | Production of triisocynatosilane |
| JP2000247982A (en) | 1999-02-26 | 2000-09-12 | Matsumoto Seiyaku Kogyo Kk | Production of isocyanatodisiloxane |
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| WO2021020325A1 (en) | 2021-02-04 |
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