CN114174307A - Composition containing silicon isocyanate compound and method for producing same - Google Patents
Composition containing silicon isocyanate compound and method for producing same Download PDFInfo
- Publication number
- CN114174307A CN114174307A CN202080052675.4A CN202080052675A CN114174307A CN 114174307 A CN114174307 A CN 114174307A CN 202080052675 A CN202080052675 A CN 202080052675A CN 114174307 A CN114174307 A CN 114174307A
- Authority
- CN
- China
- Prior art keywords
- silicon
- compound
- isocyanate compound
- composition containing
- isocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- -1 silicon isocyanate compound Chemical class 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 239000012948 isocyanate Substances 0.000 claims abstract description 40
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 34
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 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
- 238000006243 chemical reaction Methods 0.000 description 31
- 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 21
- CQGUCUVIZJHFOA-UHFFFAOYSA-N [Si+4].[N-]=C=O.[N-]=C=O.[N-]=C=O.[N-]=C=O Chemical compound [Si+4].[N-]=C=O.[N-]=C=O.[N-]=C=O.[N-]=C=O CQGUCUVIZJHFOA-UHFFFAOYSA-N 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 10
- 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
- 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
- 238000004821 distillation Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 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
- 239000002994 raw material Substances 0.000 description 6
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 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
- UVVUGWBBCDFNSD-UHFFFAOYSA-N tetraisocyanatosilane Chemical compound O=C=N[Si](N=C=O)(N=C=O)N=C=O UVVUGWBBCDFNSD-UHFFFAOYSA-N 0.000 description 5
- VCAQNZRCMTWIQO-UHFFFAOYSA-N triisocyano(methyl)silane Chemical compound C[Si]([N+]#[C-])([N+]#[C-])[N+]#[C-] VCAQNZRCMTWIQO-UHFFFAOYSA-N 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
- 239000002808 molecular sieve Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-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
- 125000005843 halogen 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
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-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
- 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000000746 purification Methods 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
- 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
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-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
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-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
- 229910021578 Iron(III) chloride Inorganic materials 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
- 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
- 150000003973 alkyl amines Chemical class 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
- 239000002585 base Substances 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
- 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
- 235000011089 carbon dioxide Nutrition 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
- 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
- 230000000694 effects Effects 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
- 125000002485 formyl group Chemical group [H]C(*)=O 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
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 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
- 239000003208 petroleum Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 238000007670 refining 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
- 239000005720 sucrose Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 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
- 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
- 229920002554 vinyl polymer Polymers 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
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention provides a method for producing a composition containing a silicon isocyanate compound, which is high in purity of a monomer of the silicon isocyanate compound, at low cost on an industrial scale. A process comprising the steps (A) to (D) of reacting a halogenated silicon compound with a cyanate or an isocyanate in the presence of a solvent and an alkanediol compound to produce a composition containing a silicon isocyanate compound, (A) a step of mixing the cyanate or isocyanate, an azeotropic solvent, the alkanediol compound and the solvent to form a liquid, (B) a step of heating the liquid to remove water and the azeotropic solvent, (C) a step of adding the halogenated silicon compound to the liquid to form the silicon isocyanate compound, and (D) a step of heating the liquid to distill off and recover the silicon isocyanate compound.
Description
Technical Field
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, which is characterized by performing a dehydration step using an azeotropic solvent.
Background
The silicon isocyanate compound is easily reacted with a compound containing an active hydrogen in the molecule, such as an alcohol, a primary amine, a secondary amine, or a carboxylic acid, and is therefore used as a modifier for a polymer. In addition, the silicon isocyanate compound can be easily introduced as a component of a polymer, and can impart characteristics of silicon to industrial materials. In addition, since the silicon isocyanate compound reacts rapidly with water, it reacts with moisture in the air, adsorbed water present on the surface of glass, ceramics, metal, or the like, and a silicon oxide coating having high adhesion is formed.
As a method for producing a silicon isocyanate compound, there are known: a method for producing a halogenated silane compound having an Si — X (X represents a halogen) bond by reacting a halogenated silane compound with a cyanate or an isocyanate in the presence of a solvent in the presence of an alkylamine, nitroalkane, or crown ether (patent document 1); or a method of reacting a halogenated silane compound with a cyanate or an isocyanate in the presence of an alkanediol compound (patent document 2).
Further, known are: a method of producing a hexaorganodisilazane by reacting a carbonic acid gas with a hexaorganodisilazane in the presence of ferric chloride (patent document 3); a method for producing trichlorosilane by reacting trichlorosilane with cyanic acid base in an organic solvent containing at least acetonitrile (patent document 4); a method for producing the compound by reacting an organotin isocyanate with an organosilicon compound having an active halogen atom (patent document 5).
On the other hand, it is known that a silicon isocyanate compound forms a dimer compound or an oligomer compound by a reaction with water (for example, patent document 6), and when water is mixed into a reaction system, the purity of (a monomer of) the silicon isocyanate compound is lowered.
Therefore, in order to obtain a high-purity monomer of the silicon isocyanate compound, it is necessary to sufficiently remove water from the compound to be a raw material.
In the examples of patent document 2, a dehydrated cyanate or isocyanate is used to produce a silicon isocyanate compound, but a halogenated silane compound reacts with water contained before reacting with a cyanate or isocyanate unless the solvent used or another compound used in the reaction of an alkanediol is dehydrated.
As a method for dehydrating cyanate or isocyanate, a method of dehydrating cyanate or isocyanate by heating under reduced pressure with direct fire is known, but 2 steps of a dehydration step by heating and a reaction step are required. In addition, it is difficult to manufacture the pot by a process of heating the pot with direct fire in consideration of the implementation in the industrial level. In addition, it is difficult to obtain a cyanate or isocyanate after dehydration uniformly.
In the method of patent document 2, when the reaction accelerator and the solvent are heated by direct fire, it is difficult to dehydrate the reaction accelerator and the solvent while avoiding thermal decomposition.
Other dehydration methods include dehydration methods using a solid adsorbent such as molecular sieve, activated clay, silica gel, or the like. However, since a solution containing cyanate or isocyanate, a reaction accelerator, and a solvent is in a slurry state, it is difficult to separate only the solid adsorbent from the mixed solution. When the solid adsorbent is reacted with the halogenated silane compound in a state where the solid adsorbent remains, the reaction with water contained in the solid adsorbent may cause a decrease in yield and/or purity.
In order to obtain a higher quality silicon oxide coating, a composition containing a silicon isocyanate compound having a high monomer purity is required, and therefore, development of a novel production method for producing the composition containing a silicon isocyanate compound is required.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent application laid-open No. Sho 56-26895
[ patent document 2] Japanese patent application laid-open No. S62-167785
[ patent document 3] Japanese patent application laid-open No. Sho 54-119419
[ patent document 4] Japanese patent application laid-open No. 7-188257
[ patent document 5] Japanese patent application laid-open No. Sho 55-102589
[ patent document 6] Japanese patent application laid-open No. 2000-247982.
Disclosure of Invention
(problems to be solved by the invention)
The present invention has been made in view of the above-mentioned background art, and an object of the present invention is to provide a method for producing a high-purity composition containing a silicon isocyanate compound, which can be carried out on an industrial scale and can produce a composition containing a silicon isocyanate compound at low cost.
(means for solving the problems)
The present inventors have made extensive studies to solve the above problems, and as a result, have found that a problem of a decrease in the purity of a monomer of a silicon isocyanate compound due to the mixing of water, which has been a problem in the conventional production method, can be solved by adding an azeotropic solvent to a liquid containing a cyanate or an isocyanate and an alkylene glycol compound before adding a halogenated silane compound, and performing a dehydration step by azeotropy of the azeotropic solvent with water, in a method for producing a composition containing a silicon isocyanate compound by reacting the halogenated silane compound with a cyanate or an isocyanate in the presence of an alkylene glycol compound, and thus have completed the present invention.
That is, the present invention provides a method for producing a composition containing a silicon isocyanate compound, which comprises the steps (a) to (D) described below, wherein a silicon halide compound is reacted with a cyanate or an isocyanate in the presence of a solvent and an alkanediol compound to produce the silicon isocyanate compound.
(A) A step of mixing the cyanate or isocyanate, an azeotropic solvent, the alkylene glycol compound, and the solvent to form a liquid,
(B) a step of heating the liquid to remove water and the azeotropic solvent,
(C) a step of adding the halogenated silicon compound to the liquid to form the silicon isocyanate compound, and
(D) heating the liquid to distill and recover the silicon isocyanate compound.
The present invention also provides a composition containing a silicon isocyanate compound, which contains 80% by mass or more of the silicon isocyanate compound.
The present invention also provides a method for producing a silicon oxide or silicon oxide coating film, using the composition containing a silicon isocyanate compound produced by the method for producing a composition containing a silicon isocyanate compound as a silicon precursor.
(Effect of the invention)
According to the present invention, a method for producing a composition containing a silicon isocyanate compound, which contains a high-purity monomer of the silicon isocyanate compound, can be provided. Specifically, the present invention provides a composition containing a silicon isocyanate compound, wherein the purity of the monomer of the silicon isocyanate compound is 80 mass% or more in the stage before purification.
Further, the method of the present invention can be carried out on an industrial scale, and a composition containing a silicon isocyanate compound can be produced at low cost.
Detailed Description
The present invention will be described below, but the present invention is not limited to the following embodiments and can be implemented by being modified as desired.
The method for producing the composition containing a silicon isocyanate compound of the present invention is a method for producing a silicon isocyanate compound by reacting a halogenated silicon compound with a cyanate or an isocyanate in the presence of a solvent and an alkanediol compound.
Silicon isocyanate
The "silicon isocyanate compound" refers to the entire compound in which silicon (Si) and an isocyanate group (-N ═ C ═ O) are directly bonded to each other.
Among the silicon isocyanate compounds, in particular, a monomer (monomer) having only 1 silicon atom in the molecule, that is, a silicon isocyanate compound is suitable for production by the production method of the present invention.
Examples of the monomer of the silicon isocyanate compound include compounds represented by the following formula (1).
Rn(OR)mSi(NCO)4-n-m (1)
In formula (1), R is a hydrocarbon group which may be substituted, and in the case where a plurality of R are present, each R may be different. n and m are each an integer of 0 to 3 inclusive, and the sum of n and m is an integer of 0 to 3 inclusive.
R may be saturated or unsaturated, or may have an aromatic ring. Specific examples of R include: methyl, ethyl, propyl, butyl, octyl, decyl, stearyl, behenyl, vinyl (but limited to the case where m ═ 0), allyl, propargyl, phenyl, naphthyl, benzyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, butoxydiglycolathyl, pentafluoroethyl, heptafluoropropyl, and the like.
Among the monomers of the silicon isocyanate compound represented by the above formula (1), the compound represented by the following formula (1a) is required to have a precursor of a silicon oxide coating film and the like in various applications, and is particularly suitable for producing a high purity by the production method of the present invention.
RnSi(NCO)4-n (1a)
The specific compound names of the monomers of the silicon isocyanate compound produced by the production method of the present invention are as follows: tetraisocyanatosilane, methyltriisocyanosilane, ethyltriisocyanatosilane, dimethyldiisocyanatosilane, diethyldiisocyanatosilane, trimethylisocyanatosilane, triethylisocyanatosilane, and the like, and precursors having silicon oxide coatings and the like thereof are required for various applications, and particularly preferred as the applicable object of the present invention which can produce them with high purity.
Halogenated silicon compounds
The halogenated silicon compound is a raw material for producing a silicon isocyanate compound by a reaction with a later-described cyanate or isocyanate.
The "halogenated silicon compound" is a compound containing silicon and a halogen bonded to the silicon.
Although not particularly limited, typical examples of the halogenated silicon compound include compounds represented by the following formula (2).
Rn(OR)mSiX4-n-m (2)
In formula (2), R is a hydrocarbon group which may be substituted, and in the case where a plurality of R are present, each R may be different. X is halogen. n and m are each an integer of 0 to 3 inclusive, and the sum of n and m is an integer of 0 to 3 inclusive.
R in the formula (2) may be saturated or unsaturated, or may have an aromatic ring. Specific examples of R in the formula (2) are the same as those of R in the formula (1).
X in the formula (2) is more preferably chlorine (Cl), bromine (Br) or iodine (I), and particularly preferably chlorine or bromine.
Specific examples of the halogenated silicon compound represented by the formula (2) include: tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, tetrabromosilane, methyltrobromosilane, ethyltribromosilane, dimethyldibromosilane, diethyldibromosilane, trimethylbromosilane, triethylbromosilane, and the like.
Cyanate and isocyanate
The cyanate and the isocyanate are raw materials for producing a silicon isocyanate compound by a reaction with the halogenated silicon compound.
Cyanate is M (OCN)mA salt of a metal with cyanic acid (H-O-C.ident.N) represented by (M is a metal and M is a natural number). The cyanate in the production process of the present invention is preferably a salt with an alkali metal or an alkaline earth metal. The alkali metal is more preferably lithium (Li), sodium (Na), potassium (K), etc., and the alkaline earth metal is more preferably magnesium (Mg), calcium (Ca), barium (Ba), etc.
The isocyanate is selected from M (NCO)mA salt of isocyanic acid (H-N ═ C ═ O) and a metal represented by (M is a metal and M is a natural number). The isocyanate in the production method of the present invention may be exemplified by salts with silver (Ag), ammonium, and the like.
It is known that isocyanic acid (H-N ═ C ≡ O) and cyanic acid (H-O-C ≡ N) are tautomers, and usually salts such as silver and ammonium exist in the form of isocyanates, and salts such as alkali metals and lead exist in the form of cyanates. For the corresponding silicon compounds, the most part is in the form of an isocyanate of Si — N ═ C ═ O.
Among the cyanate/isocyanate, sodium cyanate, potassium cyanate and lithium cyanate are particularly preferable, and sodium cyanate is most preferable, from the practical viewpoint of easiness of availability, reactivity, easiness of handling and the like.
The cyanate or isocyanate is preferably used in an equimolar or molar excess relative to the halogen to be substituted contained in the halogenated silicon compound, and particularly preferably in an excess of 0.1 to 2 equivalents relative to the halogen.
Alkanediol compound
The silicon isocyanate compound is obtained by reacting the above-mentioned halogenated silicon compound with a cyanate or an isocyanate, but the reaction may be carried out using various reaction accelerators in order to improve the reaction yield.
In the present invention, an alkanediol compound is used as the reaction accelerator.
Examples of the alkanediol compound in the production method of the present invention include: alkanediols such as ethylene glycol, propylene glycol, butylene glycol, and octanediol; halogen substituents of alkanediols; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; halogen substitutes for polyalkylene glycols, and the like.
Further, ether derivatives or ester derivatives of polyalkylene glycols or halogen-substituted products thereof are also exemplified as the alkylene glycol-based compounds in the production process of the present invention.
The ether derivative may be a monoether derivative in which only a single terminal of the polyalkylene glycol chain is substituted with a substituent, or a diether derivative in which both terminals are substituted with substituents. Substituents of ether derivatives may be listed: a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, an oleyl group, a stearyl group, a benzyl group, or a phenyl group; furfuryl (furfurfurfuryl); a glyceryl group; and residues of cyclic polyvalent hydroxy compounds such as sorbitol and sucrose. The hydrogen atoms in these substituents may be replaced by halogen atoms.
The ester derivative may be a monoester derivative in which only a single terminal of the polyalkylene glycol chain is substituted with a substituent, or a diester derivative in which both terminals are substituted with substituents. The substituents of the ester derivative may be exemplified by: formyl, acetyl, propionyl, butyryl, benzoyl, and the like. The hydrogen atoms in these substituents may be replaced by halogen atoms.
A compound in which one end of a polyalkylene glycol chain is substituted with a substituent of the above ether derivative and the other end is substituted with a substituent of the above ester derivative can also be used as the alkylene glycol compound in the production method of the present invention.
These alkylene glycol compounds may be used alone or in combination of 2 or more depending on the desired reactivity.
Among these alkylene glycol compounds, ethylene glycol, polyethylene glycol, and various derivatives have particularly good reactivity and can be used more preferably as the reaction accelerator of the present invention.
In the present invention, since a high-purity monomer of the silicon isocyanate compound can be obtained by removing water from the reaction system by azeotropic dehydration, a compound containing no active hydrogen in the structure can be particularly preferably used among the alkanediol compounds.
The aforementioned alkanediol compound generally gives good results when calculating HLB by following the qualitative method of surfactants, and when calculating the HLB, a compound having a structure that shows at least 10.5 or more, particularly 13.5 or more, is calculated.
The amount of the alkanediol compound added is preferably 0.01 parts by mass or more, and particularly preferably 0.05 parts by mass or more, based on 100 parts by mass of the silicon halide compound. Further, it is more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less.
When the amount is not less than the lower limit, the reaction time can be sufficiently shortened to easily improve the productivity (when the amount is less than 0.01 part by mass, the time required for completion of the reaction may be not less than 5 hours). When the amount is not more than the upper limit, the yield tends to be high (for example, when the amount is more than 20 parts by mass, the reaction rate increases, and when the alkylene glycol compound has an OH group, the silicon compound reacts with the OH group, and the yield may be low).
Solvent (solvent)
In the present invention, the cyanic acid or isocyanate, the alkanediol compound and the azeotropic solvent described later are added to a solvent and mixed to produce a liquid. The liquid may be a solution in which the components are dissolved in a solvent, or a suspension such as a slurry.
After removing water from the liquid by azeotropic dehydration, a halogenated silicon compound is added to the liquid and a heating reaction is carried out, thereby obtaining a composition containing a silicon isocyanate compound.
The solvent must be one which does not deteriorate the reaction raw materials and the reaction products.
Examples of the solvent include organic solvents such as hydrocarbons and halogenated hydrocarbons. Specifically, the following can be exemplified: n-hexane, cyclohexane, petroleum ether, liquid paraffin, benzene, toluene, xylene, chloroform, trichloroethylene, 1,2, 2-tetrachloroethane, chlorobenzene, triethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, diisononyl phthalate, dibutyl phthalate, and the like.
These solvents are preferably used in an amount necessary for uniformly dissolving or dispersing the cyanate or isocyanate by stirring.
Azeotropic solvent
In the present invention, an azeotropic solvent is added to the solvent in addition to cyanic acid or isocyanate and the alkanediol compound before the reaction.
When water is present in the reaction of cyanic acid or isocyanate with the silicon halide compound, the silicon isocyanate compound is reacted with the silicon halide compound or with the silicon isocyanate compound which is a product to form a silicon isocyanate compound having more than a dimer, which results in a decrease in purity and a decrease in yield of the silicon isocyanate compound monomer. Water is contained as an impurity in isocyanic acid or an isocyanate, a reaction accelerator (an alkylene glycol compound), and a solvent.
In the present invention, an azeotropic solvent is added to the solvent to remove the water contained therein, thereby performing azeotropic dehydration.
In the present invention, as compared with a method of dehydrating a cyanate or an isocyanate as a raw material in advance as in patent document 2, since water can be sufficiently removed, a silicon isocyanate compound-containing composition having a high purity of a silicon isocyanate compound monomer can be obtained.
The azeotropic solvent is required to be a solvent which does not deteriorate the reaction raw material or the reaction product. Examples of the azeotropic solvent include organic solvents containing no active hydrogen in the chemical structure.
The azeotropic solvent is preferably a hydrocarbon, and particularly preferably an aromatic hydrocarbon. Specific examples of the compound include: benzene, toluene, xylene, ethylbenzene, and the like.
The azeotropic solvent may be used alone in 1 kind or in combination of 2 or more kinds.
The method for producing the composition containing a silicon isocyanate compound of the present invention has the following steps (a) to (D).
[ step (A) ]
In the step (A), the isocyanate or isocyanic acid, the azeotropic solvent, the alkanediol compound and the solvent are mixed to form a liquid. The liquid may be a solution in which the components are dissolved in a solvent, or a suspension such as a slurry.
In the step (a), the order of charging the components is not particularly limited. It is more preferable to carry out step (a) while stirring the inside of the reaction vessel so as to sufficiently mix the components.
[ step (B) ]
In step (B), the liquid produced in step (a) is heated to remove water and azeotropic solvent. By carrying out the step (B), water is removed from the liquid, and as a result, when the cyanate or the isocyanic acid reacts with the halogenated silicon compound, the polymerization reaction caused by the reaction with water can be prevented, and a composition containing a silicon isocyanate compound having a high purity of the silicon isocyanate compound monomer can be obtained.
In the step (B), the conditions for azeotropic dehydration are not particularly limited, but it is more preferable to perform azeotropic dehydration under normal pressure, then reduce the pressure, and further perform azeotropic dehydration.
The liquid temperature at the time of azeotropic dehydration under normal pressure is preferably 20 ℃ or higher, more preferably 50 ℃ or higher, and particularly preferably 100 ℃ or higher. Further, it is preferably 250 ℃ or lower, more preferably 230 ℃ or lower, and particularly preferably 200 ℃ or lower.
When the liquid temperature is in the above range, the composition containing the silicon isocyanate compound can be produced without lowering the purity of the silicon isocyanate compound monomer and the yield.
The liquid temperature when azeotropic dehydration is performed under normal pressure, then reduced pressure, and further azeotropic dehydration is performed is preferably 20 ℃ or higher, more preferably 50 ℃ or higher, and particularly preferably 100 ℃ or higher. Further, it is preferably 250 ℃ or lower, more preferably 230 ℃ or lower, and particularly preferably 200 ℃ or lower.
The degree of reduced pressure (pressure) is preferably 0.1kPa or more, more preferably 0.3kPa or more, and particularly preferably 0.5kPa or more. Further, it is preferably not more than 101.3kPa, more preferably not more than 90kPa, and particularly preferably not more than 50 kPa.
When the liquid temperature and the reduced pressure (pressure) are within the above ranges, the isocyanate silicon compound-containing composition can be produced in a yield without lowering the purity of the isocyanate silicon compound monomer.
[ step (C) ]
In the step (C), the halogenated silicon compound is added to the liquid obtained by removing the water and the azeotropic solvent in the step (B), and the halogenated silicon compound is reacted with cyanic acid or an isocyanate to produce the silicon isocyanate compound.
The reaction temperature in the step (C) may be at room temperature or lower, but when it is carried out at room temperature, it takes a long time of 5 hours or more than 5 hours in many cases. On the other hand, at a temperature higher than 200 ℃, although the reaction time is short, the silicon isocyanate compound which is a product may cause a side reaction.
Therefore, the reaction temperature is preferably room temperature or higher, more preferably 50 ℃ or higher, and particularly preferably 100 ℃ or higher. Further, it is preferably 200 ℃ or lower, more preferably 190 ℃ or lower, and particularly preferably 180 ℃ or lower.
When the reaction time is less than the lower limit, the reaction can be terminated in a short time (about 2 hours at the maximum). When the amount is not more than the upper limit, the side reaction of the silicon isocyanate compound is easily suppressed.
[ step (D) ]
In the step (D), the liquid containing the silicon isocyanate compound produced in the reaction of the step (C) is heated to distill and recover the silicon isocyanate compound.
In the step (D), the liquid may be heated under normal pressure to distill the silicon isocyanate compound, or may be distilled under reduced pressure. It is also possible to extract the product by distillation initially under normal pressure and then under reduced pressure, so that the yield can be easily increased.
The liquid temperature at the time of distilling the silicon isocyanate compound under normal pressure is preferably 100 ℃ or higher, more preferably 120 ℃ or higher, and particularly preferably 150 ℃ or higher. Further, it is preferably 250 ℃ or lower, more preferably 200 ℃ or lower, and particularly preferably 190 ℃ or lower.
When the liquid temperature is in the above range, the composition containing the silicon isocyanate compound can be produced without lowering the purity of the silicon isocyanate compound monomer and the yield.
The liquid temperature when the distillation is carried out under normal pressure and then under reduced pressure is preferably 100 ℃ or higher, more preferably 120 ℃ or higher, and particularly preferably 150 ℃ or higher. Further, it is preferably 250 ℃ or lower, more preferably 200 ℃ or lower, and particularly preferably 190 ℃ or lower.
The degree of reduced pressure (pressure) is preferably 0.1kPa or more, more preferably 0.3kPa or more, and particularly preferably 0.5kPa or more. Further, it is preferably 101.3kPa or less, more preferably 90kPa or less, and particularly preferably 80kPa or less.
When the liquid temperature and the reduced pressure (pressure) are within the above ranges, the isocyanate silicon compound-containing composition can be produced in a yield without lowering the purity of the isocyanate silicon compound monomer.
In the present invention, water is removed from the liquid by azeotropic dehydration in step (B) before the reaction of the halogenated silicon compound with cyanic acid or isocyanate in step (C). Therefore, the content of the compound of dimer or more, which is an undesirable side reaction product, in the silicon isocyanate compound produced in step (C) is very small, and a large amount of the monomer is contained.
Therefore, the composition (the composition containing the isocyanatosilicon compound) recovered by distilling off the isocyanatosilicon compound in the step (D) contains a large amount of the isocyanatosilicon compound monomer.
Specifically, the composition containing a silicon isocyanate compound recovered in the step (D) usually contains 80% by mass or more of a silicon isocyanate compound monomer (purity of the silicon isocyanate compound monomer is 80% by mass or more). Further, according to the method of the present invention, in the stage of the recovery in the step (D), a composition containing a silicon isocyanate compound containing 85 mass% or more of a silicon isocyanate compound monomer or a composition containing a silicon isocyanate compound containing 90 mass% or more of a silicon isocyanate compound monomer can be obtained.
The purity of the monomeric isocyanate compound in the present specification is a value obtained by measuring the purity by gas chromatography using a hydrogen flame ionization type detector and calculating the area ratio.
[ distillation step (refining step) ]
As described above, in the method of the present invention, the isocyanate compound-containing composition having the purity of the isocyanate silicon compound monomer of 80 mass% or more can be obtained in the stage of the recovery in the step (D).
The purity of the isocyanate silicon compound monomer can be further improved (higher purity) by further heating and distilling the composition containing the isocyanate silicon compound recovered in the step (D) under normal pressure and/or reduced pressure.
The distillation may be carried out by a generally known method, and for example, a method using a rectifying column is exemplified.
In the method of the present invention, in the stage of the recovery in the step (D), since the purity of the isocyanate silicon compound monomer in the isocyanate silicon compound-containing composition is higher than that obtained by the conventional method, the purity of the isocyanate silicon compound monomer in the isocyanate silicon compound-containing composition after the distillation step is also high.
Specifically, the purity of the isocyanate silicon compound monomer in the isocyanate silicon compound-containing composition after the distillation step (purification step) is preferably 90% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, more preferably 99.1% by mass or more, and most preferably 99.5% by mass or more.
The present invention also relates to a method for producing a silicon oxide or silicon oxide coating film, which uses the composition containing a silicon isocyanate compound produced by the method for producing a composition containing a silicon isocyanate compound as a silicon precursor.
The composition containing a silicon isocyanate compound produced by the method for producing a composition containing a silicon isocyanate compound of the present invention or the composition containing a silicon isocyanate compound obtained by purifying the composition containing a silicon isocyanate compound has a high purity of the silicon isocyanate compound monomer, and therefore is suitable as a silicon precursor for producing a silicon oxide or a silicon oxide coating film.
(examples)
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples without departing from the gist thereof.
Production example 1
26.0 parts by mass (0.4 parts by mol) of sodium cyanate (manufactured by pure chemical Co., Ltd.), 0.4 part by mass of polyoxyethylene alkyl ether and 23.8 parts by mass of liquid paraffin (manufactured by Nippon Petroleum Co., Ltd., trade name: Hi-White 350) were mixed with 17.9 parts by mass of toluene, and azeotropic dehydration of toluene and water was carried out at a liquid temperature of 110 to 200 ℃ under normal pressure. Then, azeotropic dehydration was further carried out under the conditions of a liquid temperature of 200 ℃ and a reduced pressure of 3 kPa.
After azeotropic dehydration, 14.9 parts by mass (0.1 parts by mole) of methyltrichlorosilane (manufactured by tokyo chemical industry co., ltd.) was added dropwise and reacted at 170 ℃ for 1 hour, and then the liquid was distilled off at normal pressure at a liquid temperature ranging from 150 to 190 ℃ to obtain 13.5 parts by mass of a composition containing methyltriisocyanosilane having a purity of 80 mass%.
In addition, 10.0 parts by mass of the obtained composition was distilled at a liquid temperature in the range of 150 to 190 ℃ under normal pressure to obtain 5.0 parts by mass of a composition containing methyltriisocyanosilane having a purity of more than 99%.
Production example 2
After 39.8 parts by mass (0.6 parts by mol) of sodium cyanate (manufactured by pure chemical Co., Ltd.), 0.3 part by mass of polyoxyethylene alkyl ether and 26.3 parts by mass of liquid paraffin (manufactured by Nippon Petroleum Co., Ltd., trade name: Hi-White 350) were mixed with 26.3 parts by mass of ethylbenzene, azeotropic dehydration of ethylbenzene and water was carried out at a liquid temperature of 110 to 200 ℃ under normal pressure. Then, azeotropic dehydration was further carried out at a liquid temperature of 200 ℃ and a reduced pressure of 3 kPa.
After azeotropic dehydration, 17.0 parts by mass (0.1 parts by mole) of tetrachlorosilane (manufactured by tokyo chemical industry Co., Ltd.) was added dropwise and reacted at 170 ℃ for 1 hour, and then the liquid was distilled off at a liquid temperature of 160 to 180 ℃ and a reduced pressure of 60 to 80kPa to obtain 13.7 parts by mass of a composition containing tetraisocyanatosilane having a purity of 80% by mass.
In addition, 10.0 parts by mass of the obtained composition was distilled at a liquid temperature in the range of 150 to 190 ℃ under normal pressure to obtain 5.0 parts by mass of a composition containing tetraisocyanatosilane having a purity of more than 99%.
Production example 3
14.9 parts by mass (0.1 part by mol) of methyltrichlorosilane (manufactured by Tokyo chemical industry Co., Ltd.) was added dropwise to 23.8 parts by mass of sodium cyanate (manufactured by pure chemical Co., Ltd.), 0.4 part by mass of polyoxyethylene alkyl ether and liquid paraffin (manufactured by New Nippon Petroleum Co., Ltd., trade name: Hi-White 350) to react at 170 ℃ for 1 hour, and then the liquid was distilled off at normal pressure at a liquid temperature in the range of 150 to 190 ℃ to obtain 13.0 parts by mass of a composition containing methyltriisocyanosilane having a purity of 70 mass%.
In addition, 10.0 parts by mass of the obtained composition was distilled under the same conditions as in example 1 to obtain 5.0 parts by mass of a composition containing methyltriisocyanosilane having a purity of 90 mass%.
Production example 4
10.0 parts by mass of a molecular sieve was mixed with 26.0 parts by mass (0.4 parts by mol) of sodium cyanate (manufactured by PURINE CHEMICAL Co., Ltd.), 0.4 part by mass of polyoxyethylene alkyl ether, and 23.8 parts by mass of liquid paraffin (manufactured by NITILE PETROLEUM CO., LTD.: Hi-White 350), and the mixture was allowed to stand for 24 hours.
Then, although removal of the molecular sieve was attempted, the molecular sieve was in a slurry state and was mixed with sodium cyanate and could not be separated, and therefore, dehydration was not possible.
(availability in industry)
The composition containing a silicon isocyanate compound of the present invention contains a silicon isocyanate compound having an Si — NCO bond, and is easily reacted with a compound containing active hydrogen in the molecule such as an alcohol, a primary amine, a secondary amine, or a carboxylic acid, so that it is easy to introduce a modifier as a polymer or a component of a polymer to add the characteristics of silicon to an industrial material. Further, since the silicon oxide film reacts with water rapidly, the silicon oxide film reacts with moisture in the air, adsorbed water present on the surface of glass, ceramics, metal, or the like, and a silicon oxide film having high adhesion is formed.
Claims (7)
1. A method for producing a composition containing a silicon isocyanate compound, which comprises reacting a halogenated silicon compound with a cyanate or an isocyanate in the presence of a solvent and an alkanediol compound to produce a silicon isocyanate compound, wherein the method comprises the following steps (A) to (D):
(A) a step of mixing the cyanate or isocyanate, an azeotropic solvent, the alkylene glycol compound, and the solvent to form a liquid,
(B) a step of heating the liquid to remove water and the azeotropic solvent,
(C) a step of adding the halogenated silicon compound to the liquid to form the silicon isocyanate compound, and
(D) heating the liquid to distill and recover the silicon isocyanate compound.
2. The method for producing a composition containing a silicon isocyanate compound according to claim 1, wherein the azeotropic solvent is a solvent containing no active hydrogen in a chemical structure.
3. The method for producing a composition containing a silicon isocyanate compound according to claim 1, wherein the azeotropic solvent is an aromatic hydrocarbon.
4. The method for producing a composition containing a silicon isocyanate compound according to claim 1, wherein the azeotropic solvent is at least 1 solvent selected from the group consisting of toluene, xylene, and ethylbenzene.
5. The method for producing the composition containing a silicon isocyanate compound according to any one of claims 1 to 4, wherein the produced composition containing a silicon isocyanate compound contains 80% by mass or more of a monomer of a silicon isocyanate compound.
6. A composition containing a silicon isocyanate compound, which contains 80 mass% or more of a monomer of the silicon isocyanate compound.
7. A method for producing a silicon oxide or silicon oxide coating film, using, as a silicon precursor, the composition containing a silicon isocyanurate compound produced by the method for producing a composition containing a silicon isocyanurate compound according to any one of claims 1 to 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019139392 | 2019-07-30 | ||
| JP2019-139392 | 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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| CN114174307A true CN114174307A (en) | 2022-03-11 |
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| JP (1) | JPWO2021020325A1 (en) |
| KR (1) | KR20220039729A (en) |
| CN (1) | CN114174307A (en) |
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| WO (1) | WO2021020325A1 (en) |
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- 2020-07-27 CN CN202080052675.4A patent/CN114174307A/en active Pending
- 2020-07-27 JP JP2021537013A patent/JPWO2021020325A1/ja active Pending
- 2020-07-27 KR KR1020227003738A patent/KR20220039729A/en unknown
- 2020-07-27 WO PCT/JP2020/028634 patent/WO2021020325A1/en active Application Filing
- 2020-07-28 TW TW109125430A patent/TW202112789A/en unknown
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| KR20220039729A (en) | 2022-03-29 |
| JPWO2021020325A1 (en) | 2021-02-04 |
| WO2021020325A1 (en) | 2021-02-04 |
| TW202112789A (en) | 2021-04-01 |
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