JPH0229405A - Production of thermoplastic resin - Google Patents
Production of thermoplastic resinInfo
- Publication number
- JPH0229405A JPH0229405A JP17840688A JP17840688A JPH0229405A JP H0229405 A JPH0229405 A JP H0229405A JP 17840688 A JP17840688 A JP 17840688A JP 17840688 A JP17840688 A JP 17840688A JP H0229405 A JPH0229405 A JP H0229405A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- formula
- general formula
- resin
- thermoplastic resin
- 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
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- -1 N-substituted maleimide Chemical class 0.000 claims description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 14
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 abstract description 11
- 230000018044 dehydration Effects 0.000 abstract description 9
- 238000006297 dehydration reaction Methods 0.000 abstract description 9
- 150000001412 amines Chemical class 0.000 abstract description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 2
- 238000007259 addition reaction Methods 0.000 abstract 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 24
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- OCKPCBLVNKHBMX-UHFFFAOYSA-N n-butyl-benzene Natural products CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- GEJJECIDFXFUMI-UHFFFAOYSA-N dodecanethioic s-acid Chemical compound CCCCCCCCCCCC(S)=O GEJJECIDFXFUMI-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000004246 zinc acetate Substances 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
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- ZEPHQHDSAIWJAD-UHFFFAOYSA-N 1-(4-bicyclo[2.2.1]heptanyl)pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1(C2)CCC2CC1 ZEPHQHDSAIWJAD-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- SXTILEHINBCKSS-UHFFFAOYSA-N 1-chloro-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(Cl)C(=O)C=C1C1=CC=CC=C1 SXTILEHINBCKSS-UHFFFAOYSA-N 0.000 description 1
- QCOLXFOZKYRROA-UHFFFAOYSA-N 1-methoxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(OC)C(=O)C=C1C1=CC=CC=C1 QCOLXFOZKYRROA-UHFFFAOYSA-N 0.000 description 1
- IYBPIDAYDPNCTP-UHFFFAOYSA-N 1-methyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(C)C(=O)C=C1C1=CC=CC=C1 IYBPIDAYDPNCTP-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- PSABUFWDVWCFDP-UHFFFAOYSA-N 2,2-dimethylheptane Chemical compound CCCCCC(C)(C)C PSABUFWDVWCFDP-UHFFFAOYSA-N 0.000 description 1
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- UIXRDRQSWYSVNK-UHFFFAOYSA-N 2-butyl-4,6-dimethylphenol Chemical compound CCCCC1=CC(C)=CC(C)=C1O UIXRDRQSWYSVNK-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- HWMZHVLJBQTGOL-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanylmethanamine Chemical compound C1CC2C(CN)CC1C2 HWMZHVLJBQTGOL-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- UIZDKHDPZRCOBN-UHFFFAOYSA-N 3-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCC1=CC(=O)NC1=O UIZDKHDPZRCOBN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GQWWGRUJOCIUKI-UHFFFAOYSA-N Peramine Natural products O=C1N(C)C(CCCN=C(N)N)=CN2C=CC=C21 GQWWGRUJOCIUKI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- IQYMRQZTDOLQHC-ZQTLJVIJSA-N [(1R,4S)-2-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C=C)C[C@@H]1C2 IQYMRQZTDOLQHC-ZQTLJVIJSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- SKKHNUKNMQLBTJ-QIIDTADFSA-N [(1s,4r)-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C(=C)C)C[C@@H]1C2 SKKHNUKNMQLBTJ-QIIDTADFSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- JEPPYVOSGKWVSJ-UHFFFAOYSA-N bicyclo[2.2.1]heptan-3-amine Chemical compound C1CC2C(N)CC1C2 JEPPYVOSGKWVSJ-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ODEFEPURKFSBBQ-UHFFFAOYSA-N tris(sulfanylidene)-lambda6-sulfane Chemical compound S=S(=S)=S ODEFEPURKFSBBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規なN−置換マレイミドを単量体成分とし
てなる熱可塑性樹脂の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a thermoplastic resin comprising a novel N-substituted maleimide as a monomer component.
従来、汎用のプラスチックスとしては、ポリメタクリル
酸メチルが、その優れた光透過性、耐候性、耐衝撃性、
加工性及び軽量さから種々の用途に広く使用されている
が、耐熱性が十分でないため、高熱を受ける分野では使
用できないという欠点がある。Traditionally, polymethyl methacrylate has been used as a general-purpose plastic due to its excellent light transmittance, weather resistance, impact resistance,
Although it is widely used in various applications due to its workability and light weight, it has the disadvantage that it cannot be used in fields subject to high heat because it does not have sufficient heat resistance.
そこで、従来からポリメタクリル酸メチルのようなビニ
ル系熱可塑性樹脂の耐熱性を向上させるために種々のN
−置換マレイミドを共重合させる方法が提案されている
。例えば、N−フェニルマレイミドを共重合させる方法
(特公昭439753号、特開昭56−179034号
、同57−45692号、同5B−162616号、同
58−206657号公報等)、N−シクロへキシルマ
レイミドを共重合させる方法(特開昭62−15611
5号公報等)などがある。Therefore, various types of N have been used to improve the heat resistance of vinyl thermoplastic resins such as polymethyl methacrylate.
A method of copolymerizing -substituted maleimides has been proposed. For example, a method of copolymerizing N-phenylmaleimide (Japanese Patent Publication No. 439753, Japanese Patent Publication No. 56-179034, Japanese Patent Publication No. 57-45692, Japanese Patent Publication No. 5B-162616, Japanese Patent Publication No. 58-206657, etc.), Method for copolymerizing xylmaleimide (JP-A-62-15611
Publication No. 5, etc.).
しかし、ビニル系熱可塑性樹脂の耐熱性を向上させる上
記のような方法には、種々の問題があり、N−フェニル
マレイミドを共重合させる方法では、耐熱性は向上する
ものの、N−フェニルマレイミド自身が黄色であるため
、無色透明な樹脂が得られないばかりか、樹脂が著しく
着色してしまうという問題がある。また、N−シクロへ
キシルマレイミドを共重合させる方法では、はとんど着
色せず、透明性に優れた樹脂が得られるものの、耐熱性
の向上が十分でなく、満足できるものを得ることはでき
ない。However, the above methods for improving the heat resistance of vinyl thermoplastic resins have various problems.The method of copolymerizing N-phenylmaleimide improves the heat resistance, but the N-phenylmaleimide itself Since it is yellow, there is a problem that not only is it impossible to obtain a colorless and transparent resin, but the resin is also significantly colored. In addition, with the method of copolymerizing N-cyclohexylmaleimide, a resin with excellent transparency and almost no coloring can be obtained, but the heat resistance is not sufficiently improved and it is difficult to obtain a satisfactory product. Can not.
そこで、本発明者らは、耐熱性及び透明性に優れたビニ
ル系熱可塑性樹脂を開発することを課題として鋭意研究
を重ねた。その結果、特定の(メタ)アクリル酸エステ
ルに特定のN−置換マレイミドを共重合させることによ
って上記の課題が解決されることを見出し、本発明を完
成した。Therefore, the present inventors have conducted extensive research with the objective of developing a vinyl thermoplastic resin with excellent heat resistance and transparency. As a result, the inventors discovered that the above-mentioned problems could be solved by copolymerizing a specific (meth)acrylic acid ester with a specific N-substituted maleimide, and completed the present invention.
すなわち、本発明は、(A)一般式〔■〕 :〔式中R
は水素原子又は炭素原子数1〜4のアルキル基を示し、
nはO又は1である〕で表わされるN−置換マレイミド
及び
(B)一般式〔■〕 :
R+
CHz=CCORz (II)〔式
中R8は水素原子又はメチル基を示し、R2は炭素原子
数1〜5のアルキル基を示す]で表わされる(メタ)ア
クリル酸エステル
を重合させることを特徴とする熱可塑性樹脂の製造法に
関する。That is, the present invention provides (A) general formula [■]: [in the formula R
represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
n is O or 1] and (B) general formula [■]: R+ CHz=CCORz (II) [wherein R8 represents a hydrogen atom or a methyl group, and R2 represents the number of carbon atoms The present invention relates to a method for producing a thermoplastic resin characterized by polymerizing a (meth)acrylic acid ester represented by 1 to 5 alkyl groups.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に使用する前記一般式CI)で表わされるN−置
換マレイミドは、新奇な化合物であり、例えば、一般式
〔■] :
〔式中R及びnは前記のものを示す〕で表わされるアミ
ン化合物と無水マレイン酸を付加させ、−般式〔■]
:
〔式中R及びnは前記のものを示す〕で表わされるマレ
アミド酸を得た後、このマレアミド酸を脱水閉環するこ
とにより得ることができる。The N-substituted maleimide represented by the general formula CI) used in the present invention is a novel compound, for example, an amine represented by the general formula [■]: [wherein R and n are as defined above] By adding the compound and maleic anhydride, - general formula [■]
: It can be obtained by obtaining a maleamic acid represented by [wherein R and n are as defined above] and then dehydrating and ring-closing this maleamic acid.
本発明に使用するN−置換マレイミドの製造は、前記の
ように、一般式[111)で表わされるアミン化合物に
無水マレイン酸を付加させて一般式(IV)で表わされ
るマレアミド酸を生成する工程(第一工程)と、一般式
(IV)で表わされるマレアミド酸を脱水閉環して一般
式(I)で表わされるN置換マレイミドとする工程(第
二工程)に分けることができる。As mentioned above, the production of the N-substituted maleimide used in the present invention is a step of adding maleic anhydride to the amine compound represented by the general formula [111) to produce maleamic acid represented by the general formula (IV). (first step) and a step (second step) of dehydrating and ring-closing maleamic acid represented by general formula (IV) to form an N-substituted maleimide represented by general formula (I).
第一工程と第二工程は、別々に行うことも、連続的に行
うこともできるが、効率などの面から連続的に行うのが
好ましい。各工程について、以下にさらに詳しく説明す
る。Although the first step and the second step can be performed separately or continuously, it is preferable to perform them continuously from the viewpoint of efficiency. Each step will be explained in more detail below.
第一工程において、一般式(I[I)で表わされるアミ
ン化合物1モルに対して無水マレ4790.6〜1.2
モル、さらに好ましくは1モルを反応させる。これは、
反応生成物中に未反応の原料が残存しないようにするた
めである。In the first step, anhydrous male 4790.6 to 1.2
A mole, more preferably 1 mole, is reacted. this is,
This is to prevent unreacted raw materials from remaining in the reaction product.
反応に際しては、溶媒を使用することが好ましく、溶媒
としてマレイミド酸合成の際の溶媒として公知のものを
使用することができるが、第一工程と第二工程を連続的
に行うためには、脱水閉環反応で生成する水を共沸除去
でき、かつ不活性であり、反応に関与しない溶媒が好ま
しく、例えばオクタン、ノナン、デカン、ドデカン、ト
リメチルヘキサン、テトラクロルエタン、エチルシクロ
ヘキサン等のパラフィン系溶媒、ベンゼン、トルエン、
キシレン、エチルベンゼン、クメン、メシチレン、L−
ブチルベンゼン、プソイドクメン、クロルベンゼン、0
−ジクロルベンゼン、m−ジクロルベンゼン、p−ジク
ロルベンゼン、ブチルベンゼン、P−シメン、n−ブチ
ルベンゼン、5ec−ブチルベンゼン、テトラヒドロナ
フタリン、デカヒドロナフタリン、ナフタリン、シクロ
ヘキシルベンゼン等の芳香族系溶媒を使用することがで
きる。テトラヒドロナフタリン及びp−シメンが好まし
い。溶媒の使用量は、原料アミン化合物に対して1〜2
0倍量(重量)であることが好ましく、4〜10倍量(
重量)であることがより好ましい。It is preferable to use a solvent during the reaction, and known solvents for maleimide acid synthesis can be used. However, in order to perform the first and second steps continuously, dehydration Solvents that can azeotropically remove water produced in the ring-closing reaction, are inert, and do not participate in the reaction are preferred, such as paraffinic solvents such as octane, nonane, decane, dodecane, trimethylhexane, tetrachloroethane, and ethylcyclohexane; benzene, toluene,
xylene, ethylbenzene, cumene, mesitylene, L-
Butylbenzene, pseudocumene, chlorobenzene, 0
- Aromatic systems such as dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, butylbenzene, P-cymene, n-butylbenzene, 5ec-butylbenzene, tetrahydronaphthalene, decahydronaphthalene, naphthalene, cyclohexylbenzene, etc. Solvents can be used. Tetrahydronaphthalene and p-cymene are preferred. The amount of solvent used is 1 to 2 per amine compound as the raw material.
It is preferably 0 times the amount (weight), and 4 to 10 times the amount (by weight).
weight) is more preferable.
反応に際しては、アミン化合物と無水マレイン酸を始め
から全量仕込んでも良いが、発熱反応であるため、片方
を後から追加添加する方がより好ましく、さらに好まし
くは無水マレイン酸を溶媒に完全に溶解させたフラスコ
中に120°C以下、好ましくは30〜100°Cに温
度が維持されるように注意しながら、撹拌下、15〜1
20分かけてアミン化合物を滴下し、主にアミン化合物
への無水マレイン酸の付加を行い、一般式[IV)で表
わされるマレアミド酸を得ることができる。この時、添
加するアミン化合物はフラスコ内と同じ溶媒に溶解して
おいてもよい。During the reaction, the entire amount of the amine compound and maleic anhydride may be charged from the beginning, but since the reaction is exothermic, it is more preferable to add one of the two later, and more preferably, the maleic anhydride is completely dissolved in the solvent. under stirring, taking care to maintain the temperature below 120°C, preferably between 30 and 100°C, in a flask
The amine compound is added dropwise over 20 minutes, and maleic anhydride is mainly added to the amine compound to obtain maleamic acid represented by the general formula [IV]. At this time, the amine compound to be added may be dissolved in the same solvent as in the flask.
第二工程において、第一工程に使用しうる溶媒は全て使
用することができるが、第一工程と第二工程を連続的に
行うためには、第一工程で使用した溶媒をそのまま使用
することが好ましい。その使用量は、第一工程と同量で
あるため、連続的に反応を行う際には新たに溶媒を追加
しなくてもよい。In the second step, all the solvents that can be used in the first step can be used, but in order to perform the first and second steps continuously, the solvent used in the first step must be used as is. is preferred. Since the amount used is the same as that in the first step, there is no need to add a new solvent when performing the reaction continuously.
第二工程において、酸触媒として、三フッ化ホウ素等の
ルイス酸、硫酸、無水硫酸、オルソリン酸、メタリン酸
、ピロリン酸等の鉱酸、パラトルエンスルホン酸、ベン
ゼンスルホン酸、メタンスルホン酸等の有機酸、リンタ
ングステン酸、ケイタングステン酸等のへテロポリ酸な
どを使用することが好ましい。その使用量は、原料アミ
ン化合物に対して5〜150重量%であることが好まし
い。20〜100重量%であることがより好ましい。触
媒は、全量を一度に仕込んでもよいが、数回に分けて加
える方法を採用してもよい。触媒量は少ないと、反応が
進行しにくく、多すぎても、特に利点はない。反応は、
140〜270°Cに昇温しで脱水縮合(脱水閉環)さ
せるのが好ましい。In the second step, Lewis acids such as boron trifluoride, mineral acids such as sulfuric acid, sulfuric anhydride, orthophosphoric acid, metaphosphoric acid, and pyrophosphoric acid, paratoluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, etc. are used as acid catalysts. It is preferable to use organic acids, heteropolyacids such as phosphotungstic acid, silicotungstic acid, and the like. The amount used is preferably 5 to 150% by weight based on the raw material amine compound. More preferably, it is 20 to 100% by weight. The entire amount of the catalyst may be added at once, but it may also be added in several portions. If the amount of catalyst is too small, the reaction will not progress easily, and if it is too large, there is no particular advantage. The reaction is
It is preferable to carry out dehydration condensation (dehydration ring closure) by raising the temperature to 140 to 270°C.
170〜250 ’Cに昇温しで脱水縮合させるのがよ
り好ましい。この時間は、バッチの規模、触媒及び採用
される反応条件により適宜選択できる。It is more preferable to carry out dehydration condensation by raising the temperature to 170 to 250'C. This time can be selected as appropriate depending on the batch size, catalyst and reaction conditions employed.
反応に際しては、金属含有化合物として、亜鉛、クロム
、パラジウム、コバルト、ニッケル、鉄及びアルミニウ
ムよりなる群から選ばれた少なくとも1種の金属の酸化
物、酢酸塩、マレイン酸塩、コハク酸塩、硝酸塩、リン
酸塩、塩化物及び硫酸塩等を添加するのが好ましいが、
そのうち特に有効なのものは、酢酸亜鉛である。これら
の使用量は、マレアミド酸1モルに対してO,OO5〜
0.5モル%が好ましい。0.01〜0.3モル%がよ
り好ましい。In the reaction, the metal-containing compound is an oxide, acetate, maleate, succinate, or nitrate of at least one metal selected from the group consisting of zinc, chromium, palladium, cobalt, nickel, iron, and aluminum. It is preferable to add phosphates, chlorides, sulfates, etc.
Among these, zinc acetate is particularly effective. The amount of these used is O,OO5 to 1 mole of maleamic acid.
0.5 mol% is preferred. More preferably 0.01 to 0.3 mol%.
さらに安定剤として、ヒドロキノン、ヒドロキノンモノ
メチルエーテル、2,4−ジメチル−6し一ブチルフェ
ノール、p−ベンゾキノン、25−ジフェニル−p−ベ
ンゾキノン、フェノチアジン、n−ニトロソジフェニル
アミン、&Ii 塩等の重合禁止剤を50〜2000p
pm添加するのが好ましい。Furthermore, as a stabilizer, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, 2,4-dimethyl-6-monobutylphenol, p-benzoquinone, 25-diphenyl-p-benzoquinone, phenothiazine, n-nitrosodiphenylamine, &Ii salt, etc. ~2000p
It is preferable to add pm.
脱水閉環反応終了後、酸触媒を使用した場合は、水ある
いは水酸化ナトリウム、水酸化カリウム、炭酸ナトリウ
ム、炭酸水素ナトリウム等のアルカリ水溶液中で反応液
を水洗あるいは中和水洗して触媒を除去する方法、炭酸
ナトリウム、炭酸水素ナトリウム、酸化マグネシウム等
のアルカリ粉末を加え、撹拌した後、中和塩を口過して
触媒を除去する方法、あるいはトリエチルアミン、トリ
エタノールアミン、モルホリン等のアミンを加え、触媒
を中和する方法等により、酸触媒を処理することができ
る。After the completion of the dehydration ring-closing reaction, if an acid catalyst is used, remove the catalyst by washing the reaction solution in water or an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, etc., or neutralizing with water. Method: add alkali powder such as sodium carbonate, sodium bicarbonate, magnesium oxide, etc., stir, and then pass through neutralized salt to remove the catalyst; or add amine such as triethylamine, triethanolamine, morpholine, etc. The acid catalyst can be treated by methods such as neutralizing the catalyst.
脱水閉環反応終了後(酸触媒を使用した場合は上記の処
理を行う。)、反応液は、加熱域圧下に反応溶媒を除去
した後、減圧蒸留あるいは昇華精製することにより、−
a式〔IIで表わされるN置換マレイミドを高純度で得
ることができる。After the dehydration ring-closing reaction (if an acid catalyst is used, carry out the above treatment), the reaction solution is purified by vacuum distillation or sublimation after removing the reaction solvent under pressure in the heating range.
The N-substituted maleimide represented by the formula [a] can be obtained with high purity.
このようにして得ることのできるN−置換マレイミドは
、白色の結晶である。The N-substituted maleimide thus obtainable is a white crystal.
また、別途、次に述べる製造法によっても一般式(1)
で表わされるN−置換マレイミドを製造することができ
る。In addition, the general formula (1) can also be obtained by the manufacturing method described below.
An N-substituted maleimide represented by can be produced.
例えば、i)アミン化合物と無水マレイン酸を反応させ
、生成するマレアミド酸をトルエン、キシレン、クロル
ベンゼンなどの溶媒及び三硫化硫黄、硫酸、オルソリン
酸などの酸触媒と共に加熱・脱水閉環させ、この時生成
する水を溶媒との共沸により糸外に留去する製造方法、
ii)アミン化合物と無水マレイン酸とを有機溶媒中で
反応させ、生成したマレアミド酸を単離することなしに
ジメチルホルムアミド、ジメチルスルホキシドなどの非
プロトン性極性溶媒及び酸触媒の共存下に脱水閉環させ
る製造方法、山)マレアミド酸を脱水性無水カルボン酸
の存在下で第三アミンを触媒として脱水閉環する製造方
法、iv)マレアミド酸を水と共沸可能な有機溶媒中で
、酸触媒、亜鉛などの金属含有化合物及び安定剤の共存
下に170〜250°Cの範囲の反応温度で脱水閉環す
る製造方法などがあげられる。iv)の製造方法が好ま
しい。For example, i) an amine compound and maleic anhydride are reacted, and the resulting maleamic acid is heated and dehydrated and ring-closed with a solvent such as toluene, xylene, or chlorobenzene, and an acid catalyst such as sulfur trisulfide, sulfuric acid, orthophosphoric acid; A production method in which the produced water is distilled out of the yarn by azeotropy with a solvent,
ii) An amine compound and maleic anhydride are reacted in an organic solvent, and the generated maleamic acid is dehydrated and ring-closed in the coexistence of an aprotic polar solvent such as dimethylformamide or dimethyl sulfoxide and an acid catalyst without isolation. Production method, yama) A production method in which maleamic acid is dehydrated and ring-closed using a tertiary amine as a catalyst in the presence of a dehydrating carboxylic anhydride, iv) Maleamic acid is prepared in an organic solvent capable of azeotroping with water, using an acid catalyst, zinc, etc. Examples include a production method in which dehydration and ring closure are carried out at a reaction temperature in the range of 170 to 250°C in the coexistence of a metal-containing compound and a stabilizer. The production method iv) is preferred.
本発明に使用される一般式(n)で表わされる(メタ)
アクリル酸エステルとしては、例えばアクリル酸メチル
、アクリル酸エチル、アクリル酸n−プロピル、アクリ
ル酸イソプロピル、アクリル酸n−ブチル、アクリル酸
n−ペンチル、メタクリル酸メチル、メタクリル酸エチ
ル、メタクリルMn−プロピル、メタクリル酸イソプロ
ピル、メタクリル酸n−ブチル、メタクリル酸n−ペン
チルなどが挙げられる。これらのうち、透明性、耐熱性
、成形性、強度などの面からメタクリル酸メチルが好ま
しい。(Meta) represented by general formula (n) used in the present invention
Examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-pentyl acrylate, methyl methacrylate, ethyl methacrylate, Mn-propyl methacrylate, Examples include isopropyl methacrylate, n-butyl methacrylate, and n-pentyl methacrylate. Among these, methyl methacrylate is preferred from the viewpoint of transparency, heat resistance, moldability, strength, etc.
上記のようなN−置換マレイミドと(メタ)アクリル酸
エステルを共重合させて熱可塑性樹脂を得る際には、必
要に応じて、これらと重合可能な他の重合性単量体を配
合して共重合させることができる。When copolymerizing the above-mentioned N-substituted maleimide and (meth)acrylic acid ester to obtain a thermoplastic resin, other polymerizable monomers that can be polymerized with these may be blended as necessary. Can be copolymerized.
本発明において、他の重合性単量体としては、一般式(
[IIに包含されない不飽和脂肪酸エステル、芳香族ビ
ニル化合物、シアン化ビニル化合物、一般式(1)に包
含されないN−置換マレイミド等がある。In the present invention, other polymerizable monomers include general formula (
[There are unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds, N-substituted maleimides not included in general formula (1), etc. that are not included in II.
−a式(II)に包含されない不飽和脂肪酸エステルと
しては、アクリル酸ヘキシル、アクリル酸2−エチルヘ
キシル等のアクリル酸アルキルエステル、アクリル酸シ
クロヘキシル、アクリル酸トリシクロ(5,2,1,0
”°6〕デカー8−イル、アクリル酸イソボルニル、ア
クリル酸ノルボルニル等のアクリル酸シクロアルキルエ
ステル、アクリル酸フェニル、アクリル酸ベンジル等の
アクリル酸芳香族エステル、アクリル酸グリシジル等の
アクリル酸エステル、メタクリル酸ヘキシル、メタクリ
ル酸2−エチルヘキシル等のメタクリル酸アルキルエス
テル、メタクリル酸シクロヘキシル、メタクリル酸トリ
シクロ(5,2,1,0”°b〕デカー8イル、メタク
リル酸イソボルニル、メタクリル酸ノルボルニル等のメ
タクリル酸シクロアルキルエステル、メタクリル酸フェ
ニル、メタクリル酸ベンジル等のメタクリル酸芳香族エ
ステル、メタクリル酸グリシジル等のメタクリル酸エス
テル等がある。-a Unsaturated fatty acid esters not included in formula (II) include acrylic acid alkyl esters such as hexyl acrylate and 2-ethylhexyl acrylate, cyclohexyl acrylate, and tricyclo(5,2,1,0
"°6] Acrylic acid cycloalkyl esters such as decar-8-yl, isobornyl acrylate, norbornyl acrylate, acrylic acid aromatic esters such as phenyl acrylate and benzyl acrylate, acrylic acid esters such as glycidyl acrylate, methacrylic acid methacrylic acid alkyl esters such as hexyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, cycloalkyl methacrylate such as tricyclo(5,2,1,0''°b]decar-8yl methacrylate, isobornyl methacrylate, norbornyl methacrylate) Examples include esters, aromatic methacrylic esters such as phenyl methacrylate and benzyl methacrylate, and methacrylic esters such as glycidyl methacrylate.
芳香族ビニル化合物としては、α−メチルスチレン、α
−エチルスチレン等のα−置換スチレン、クロロスチレ
ン、ビニルトルエン、t−7’チルスチレン等の核置換
スチレンがある。Examples of aromatic vinyl compounds include α-methylstyrene, α
There are α-substituted styrenes such as -ethylstyrene, nuclear substituted styrenes such as chlorostyrene, vinyltoluene, and t-7'tylstyrene.
また、シアン化ビニル化合物としては、アクリロニトリ
ル、メタクリロニトリル等がある。Furthermore, examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.
一般式(1)に包含されないN−置換マレイミドとして
は、N−メチルマレイミド、N−エチルマレイミド、N
−イソプロピルマレイミド、Nブチルマレイミド、N−
ラウリルマレイミド等の脂肪族N−置換マレイミド、N
−シクロへキシルマレイミド等の脂環式N−置換マレイ
ミド、Nフェニルマレイミド、N−メチルフェニルマレ
イミド、N−クロロフェニルマレイミド、N−メトキシ
フェニルマレイミド等の芳香族N−置換マレイミド等が
挙げられる。Examples of N-substituted maleimides not included in general formula (1) include N-methylmaleimide, N-ethylmaleimide, N-
-isopropylmaleimide, N-butylmaleimide, N-
Aliphatic N-substituted maleimides such as lauryl maleimide, N
Examples include alicyclic N-substituted maleimides such as -cyclohexylmaleimide, aromatic N-substituted maleimides such as N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, and N-methoxyphenylmaleimide.
耐熱性及び透明性に優れ、かつ成形性も良好な熱可塑性
樹脂を得るためには、重合させる溶液が−C式(1〕の
N−置換マレイミドを5〜60重量%含有しているのが
好ましい。N−置換マレイミドの量が少なすぎると、上
記の効果を十分に達成することが困難となり、また、多
すぎると、成形性が悪化する傾向がある。また、重合さ
せる溶液が一般式(INで表わされる(メタ)アクリル
酸エステルを95重量%以下含有していることが好まし
い。多すぎると、耐熱性に劣る傾向がある。In order to obtain a thermoplastic resin with excellent heat resistance and transparency and good moldability, it is necessary that the polymerization solution contains 5 to 60% by weight of the N-substituted maleimide of the -C formula (1). Preferable. If the amount of N-substituted maleimide is too small, it will be difficult to fully achieve the above effects, and if it is too large, moldability will tend to deteriorate. Also, if the solution to be polymerized has the general formula ( It is preferable that the content of (meth)acrylic acid ester represented by IN is 95% by weight or less. If it is too large, the heat resistance tends to be poor.
また、他の重合性単量体は、重合させる溶液中に40重
量%以下含有されることが好ましい。多すぎると、成形
性及び耐熱性が悪化する傾向がある。Moreover, it is preferable that the other polymerizable monomers are contained in the polymerization solution in an amount of 40% by weight or less. If it is too large, moldability and heat resistance tend to deteriorate.
本発明になる熱可塑性樹脂を製造するには、−般式(1
)のN−置換マレイミド、一般式[11)のビニル系単
量体及び必要に応じて他の重合性単量体をラジカル重合
、イオン重合等の公知の方法で共重合させることができ
る。例えば、重合開始剤の存在下で、塊状重合法、溶液
重合法、懸濁重合法等の方法で製造することができる。In order to produce the thermoplastic resin of the present invention, the general formula (1
The N-substituted maleimide of ), the vinyl monomer of general formula [11), and other polymerizable monomers as necessary can be copolymerized by a known method such as radical polymerization or ionic polymerization. For example, it can be produced by methods such as bulk polymerization, solution polymerization, and suspension polymerization in the presence of a polymerization initiator.
重合開始剤としては、例えば過酸化ベンゾイル、過酸化
ラウロイル、ジーし一ブチルペルオキシへキサヒドロフ
タレート、t−ブチルペルオキシ2−エチルヘキサノエ
ート、1,1−ジーし一ブチルペルオキシー3.3.5
−)リメチルシクロヘキサン等の有機過酸化物、アゾビ
スイソブチロニトリル、アゾビス−4−メトキシ−24
−ジメチルバレロニトリル
7−1−カルボニトリル、アブジベンゾイル等のアブ化
合物、過硫酸カリウム、過硫酸アンモニウムに代表され
る水溶性触媒及び過酸化物あるいは過硫酸塩と還元剤の
組み合わせによるレドックス触媒等、通常のラジカル重
合に使用できるものは、いずれも使用することができる
。Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, di-butylperoxyhexahydrophthalate, t-butylperoxy-2-ethylhexanoate, 1,1-di-butylperoxy-3.3. 5
-) Organic peroxides such as limethylcyclohexane, azobisisobutyronitrile, azobis-4-methoxy-24
-Ab compounds such as dimethylvaleronitrile 7-1-carbonitrile and abdibenzoyl, water-soluble catalysts represented by potassium persulfate and ammonium persulfate, and redox catalysts using a combination of peroxides or persulfates and reducing agents, etc. Anything that can be used in normal radical polymerization can be used.
重合触媒は、単量体の総量に対して0.01〜10重量
%の範囲で使用するのが好ましい。重合調節剤としての
メルカプタン系化合物、チオグリコール、四臭化炭素、
α−メチルスチレンダイマー等が分子量調節のために必
要に応じて添加し得る。The polymerization catalyst is preferably used in an amount of 0.01 to 10% by weight based on the total amount of monomers. Mercaptan compounds, thioglycol, carbon tetrabromide as polymerization regulators,
α-methylstyrene dimer or the like may be added as necessary to adjust the molecular weight.
重合温度は、0〜200°Cの範囲で適宜選択するのが
好ましく、特に50〜150°Cであるのが好ましい。The polymerization temperature is preferably selected appropriately within the range of 0 to 200°C, particularly preferably 50 to 150°C.
溶液重合における溶媒としては、ベンゼン、トルエン、
キシレン、メチルエチルケトン、メチルイソブチルケト
ン、酢酸エチル、酢酸ブチル、ジクロルエチレン等を使
用することができる。懸濁重合は、水性媒体中で行われ
、懸濁剤及び必要に応じて懸濁助剤を添加する。懸濁剤
としては、ポリビニルアルコール、メチルセルロース、
ポリアクリルアミド等の水溶性高分子物質、リン酸カル
シウム、ピロリン酸マグネシウム等の難溶性無機物質等
がある。水溶性高分子物質は、単量体の総量に対して0
.03〜1重量%、難溶性無機物質は、単量体の総量に
対して0.05〜0.5重量%使用するのが好ましい。Solvents for solution polymerization include benzene, toluene,
Xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dichloroethylene, etc. can be used. Suspension polymerization is carried out in an aqueous medium, with the addition of suspending agents and, if necessary, suspension aids. Suspending agents include polyvinyl alcohol, methylcellulose,
Examples include water-soluble polymeric substances such as polyacrylamide, and sparingly soluble inorganic substances such as calcium phosphate and magnesium pyrophosphate. The water-soluble polymer substance is 0% based on the total amount of monomers.
.. It is preferable to use the slightly soluble inorganic substance in an amount of 0.05 to 0.5% by weight based on the total amount of monomers.
懸濁助剤としては、ドデシルベンゼンスルホン酸ナトリ
ウム等の陰イオン界面活性剤があり、懸濁剤として難溶
性無機物質を使用する場合には、懸濁助剤を併用するの
が好ましい。Suspending aids include anionic surfactants such as sodium dodecylbenzenesulfonate, and when a sparingly soluble inorganic substance is used as a suspending agent, it is preferable to use a suspending aid in combination.
懸濁助剤は、単量体の総量に対して0.001〜0、0
2重足%使用するのが好ましい。The suspension aid is 0.001 to 0.0 based on the total amount of monomers.
Preferably, 2% is used.
また、本発明になる熱可塑性樹脂は、他のゴム状重合体
にグラフト重合させて使用することもできる。Further, the thermoplastic resin of the present invention can also be used by graft polymerizing other rubbery polymers.
本発明になる熱可塑性樹脂には、熱可塑性樹脂の劣化防
止、成形性の向上の観点からフェノール系、チオエーテ
ル系、ホスファイト系等の抗酸化剤、滑剤、帯電防止剤
、紫外線吸収剤等を必要に応じて添加してもよい。The thermoplastic resin of the present invention contains antioxidants such as phenol-based, thioether-based, and phosphite-based antioxidants, lubricants, antistatic agents, ultraviolet absorbers, etc. from the viewpoint of preventing deterioration of the thermoplastic resin and improving moldability. It may be added if necessary.
本発明になる熱可塑性樹脂は、光学用樹脂として光学的
素子の原料となる他、一般の成形材料、塗膜材料等にも
使用することができる。The thermoplastic resin of the present invention can be used as a raw material for optical elements as an optical resin, and can also be used as a general molding material, coating material, etc.
上記の光学的素子としては、プラスチンクレンズ、プリ
ズム等の光学部材、オーディオディスク、ビデオディス
ク、情報用ディスク等の情報記録用媒体又はそのための
基板などの光学機器用素子、自動車のヘンドライド、テ
ールライ1−等の透光部材(カバー)、自動車等のメー
ター表示器のカバ、浴室用密閉型照明器具の透光部材(
カバー)などの照明器具用部材等がある。The above-mentioned optical elements include optical members such as plastic lenses and prisms, information recording media such as audio discs, video discs, and information discs, or optical equipment elements such as substrates therefor, and automobile hendroid and taillight 1. Translucent materials (covers) such as -, covers for meter displays in automobiles, etc., transparent materials (covers) for closed lighting fixtures for bathrooms, etc.
There are parts for lighting equipment such as covers).
〔実施例]
以下に実施例をあげて本発明を具体的に説明するが、本
発明はこれに限定されるものではない。[Example] The present invention will be specifically explained with reference to Examples below, but the present invention is not limited thereto.
合成例1
〔N−ノルボルニルメチルマレイミドの合成〕撹拌機、
温度計、滴下ロート及び油水分離器付き還流冷却管を取
り付けた1 000 mlのガラス製画つロフラスコ中
に無水マレイン酸49.98 g(0,51モル)及び
p−シメン49.98 gを仕込み、撹拌しながら昇温
し、約60°Cで無水マレイン酸をp−シメンに完全に
溶解させた後、フラスコ内の温度が100°C以下に維
持されるように注意しながらノルボルニルメチルアミン
63.75 g(0,51モル)をp−シメン382.
5 gに?容解した溶液を撹拌下に1時間かけて滴下し
て、N−ノルボルニルメチルマレイミド酸のp−シメン
のスラリー液を合成した。Synthesis Example 1 [Synthesis of N-norbornylmethylmaleimide] Stirrer,
49.98 g (0.51 mol) of maleic anhydride and 49.98 g of p-cymene were placed in a 1,000 ml glass funnel flask equipped with a thermometer, a dropping funnel, and a reflux condenser with an oil-water separator. After raising the temperature with stirring to completely dissolve maleic anhydride in p-cymene at about 60°C, add norbornylmethyl while being careful to maintain the temperature in the flask below 100°C. 63.75 g (0.51 mol) of amine was mixed with 382.7 g (0.51 mol) of p-cymene.
5g? The dissolved solution was added dropwise over 1 hour while stirring to synthesize a slurry of p-cymene in N-norbornylmethylmaleimide acid.
次に、上記スラリー液にオルソリン酸45.5g。Next, 45.5 g of orthophosphoric acid was added to the slurry liquid.
酢酸亜鉛0.3774g、ヒドロキノン0.0569g
及び塩化第二銅0.0569 gを加えた後、昇温した
ところ、フラスコ内の温度が約150°Cになった時点
で水がp−シメンと一緒に留出し始めた。Zinc acetate 0.3774g, hydroquinone 0.0569g
After adding 0.0569 g of cupric chloride, the temperature was raised, and when the temperature inside the flask reached about 150°C, water began to distill out together with p-cymene.
その後、さらに昇温し、約180°Cで反応により生成
する水をp−シメンと共に系外に留出させながら7時間
反応させた。反応終了後、下層に沈殿した酸触媒層を分
離除去した。Thereafter, the temperature was further raised to about 180°C, and the reaction was carried out for 7 hours while distilling water produced by the reaction out of the system together with p-cymene. After the reaction was completed, the acid catalyst layer precipitated in the lower layer was separated and removed.
続いて、反応液にイオン交換水200 mlを加え、約
60°Cで30分間撹拌水洗し、水層を分離除去した。Subsequently, 200 ml of ion-exchanged water was added to the reaction solution, and the mixture was stirred and washed with water at about 60° C. for 30 minutes, and the aqueous layer was separated and removed.
この操作をもう一度繰り返した後、反応液を21の分液
ロートに移し、イオン交換水で水洗を繰り返して触媒を
完全に除去した。その後、残存した微量の水分を除去す
るために、水洗後の反応液中に無水硫酸ナトリウムを加
え、十分に撹拌した後、口過により硫酸ナトリウムを除
去した。After repeating this operation once more, the reaction solution was transferred to a 21 separatory funnel and washed repeatedly with ion-exchanged water to completely remove the catalyst. Thereafter, in order to remove a trace amount of water remaining, anhydrous sodium sulfate was added to the reaction solution after washing with water, and after sufficient stirring, the sodium sulfate was removed by filtration.
この水洗及び脱水処理後の反応液に新たにヒドロキノン
0.0569 g及び塩化第二銅0.0569 gを加
えた後、エバポレーターにかけ、溶媒p−シメンを完全
に除去し、薄茶色結晶を得た。After water washing and dehydration, 0.0569 g of hydroquinone and 0.0569 g of cupric chloride were newly added to the reaction solution, which was then subjected to an evaporator to completely remove the solvent p-cymene to obtain light brown crystals. .
次に、上記のようにして得られた薄茶色結晶を80〜1
10°C10,1馴Hgで昇華精製し、白色結晶62.
7 gを得た。Next, the light brown crystals obtained as described above were
Purified by sublimation at 10°C with 10.1 Hg to give white crystals 62.
7 g was obtained.
得られた白色結晶の分析結果を以下に示す。The analysis results of the obtained white crystals are shown below.
まず、元素分析を行ったところ、下記のとおりであった
。First, elemental analysis was performed and the results were as follows.
元素 CHO
理論値(%) 70.22 7.37 6.8
2実測値(%) ?0.15 7.45 6.
76また、重クロロホルムを溶媒として’H−NMRス
ペクトルを分析したところ、ノルボルニル基のシグナル
が1.0〜2.4 ppra付近、ノルボルニルメチル
アミンに基づくメチレンのシグナルが3.1〜3.6
ppm付近、無水マレイン酸に基づくオレフィン性二重
結合のシグナルが6.65 ppm付近に存在し、この
プロトンの積分強度比を測定したところ、11:2:2
であった。この’H−NMRスペクトルを第1図に示す
。Element CHO Theoretical value (%) 70.22 7.37 6.8
2 Actual measurement value (%)? 0.15 7.45 6.
76 Furthermore, when we analyzed the 'H-NMR spectrum using deuterated chloroform as a solvent, the signal of the norbornyl group was around 1.0 to 2.4 ppra, and the signal of methylene based on norbornylmethylamine was around 3.1 to 3.5 ppra. 6
ppm, a signal of an olefinic double bond based on maleic anhydride was present at around 6.65 ppm, and when the integrated intensity ratio of this proton was measured, it was 11:2:2.
Met. This 'H-NMR spectrum is shown in FIG.
以上の分析結果から、得られた白色結晶は、N−ノルボ
ルニルメチルマレイミドであることが確認された。From the above analysis results, it was confirmed that the obtained white crystals were N-norbornylmethylmaleimide.
合成例2
〔N−ノルボルニルマレイミドの合成〕合成例1と同様
のフラスコに、無水マレイン酸49.98g(0,51
モル)及びP−シメン49.98gを仕込み、撹拌しな
から昇温し、約60°Cで無水マレイン酸をp−シメン
に完全に溶解させた後、フラスコ内の温度が100°C
以下に維持されるように注意しなから2−アミノノルボ
ルナン56.61g(0,51モル)をp−シメン33
9.7 gに溶解した溶液を、撹拌下に1時間かけて滴
下して、Nノルボルニルマレアミド酸のp−シメン中の
スラリー液を製造した。Synthesis Example 2 [Synthesis of N-norbornylmaleimide] Into the same flask as in Synthesis Example 1, 49.98 g of maleic anhydride (0.51
mol) and 49.98 g of P-cymene were charged, the temperature was raised without stirring, and the maleic anhydride was completely dissolved in p-cymene at about 60°C, and then the temperature inside the flask was raised to 100°C.
56.61 g (0.51 mol) of 2-aminonorbornane was added to 33 g of p-cymene, taking care to maintain a
A solution in which 9.7 g of N-norbornyl maleamic acid was dissolved in p-cymene was added dropwise over 1 hour while stirring to prepare a slurry of N-norbornyl maleamic acid in p-cymene.
次に、上記スラリー液にオルソリン酸42.6 g、酢
酸亜鉛0.3519g、ヒドロキノン0.0533g及
び塩化第二銅0.0533 gを加えた後、昇温し、合
成例1と同様の反応、後処理及び精製を行い、白色結晶
58.6 gを得た。Next, after adding 42.6 g of orthophosphoric acid, 0.3519 g of zinc acetate, 0.0533 g of hydroquinone, and 0.0533 g of cupric chloride to the slurry liquid, the temperature was raised, and the same reaction as in Synthesis Example 1 was carried out. After post-treatment and purification, 58.6 g of white crystals were obtained.
重クロロホルムを溶媒として’H−NMRスペクトルを
分析したところ、ノルボルニル基のシグナルが1.0〜
2.4 ppm付近、ノルボルニル基のマレイミドで置
換された位置のプロトンのシグナルが3.9ppm付近
、無水マレイン酸に基づくオレフィン性二重結合のシグ
ナルが5.6 ppm付近に存在し、このプロトンの積
分強度比を測定したところ、10:1:2であった。こ
の’H−NMRスペクトルを第2図に示す。When 'H-NMR spectrum was analyzed using deuterated chloroform as a solvent, the signal of norbornyl group was 1.0~
The signal of the proton at the position substituted with maleimide of the norbornyl group is present at around 2.4 ppm, the signal of the proton at the position substituted with maleimide of the norbornyl group is present at around 3.9 ppm, and the signal of the olefinic double bond based on maleic anhydride is present at around 5.6 ppm. When the integrated intensity ratio was measured, it was 10:1:2. This 'H-NMR spectrum is shown in FIG.
以上の分析結果から、得られた白色結晶はN−ノルボル
ニルマレイミドであることが確認された。From the above analysis results, it was confirmed that the obtained white crystals were N-norbornylmaleimide.
実施例1
三方活栓を備えた500成の三角フラスコに合成例1で
得られたN−ノルボルニルメチルマレイミド10g、メ
タクリル酸メチル90g、過酸化ラウロイル084g及
びラウロイルメルカプタン0.2gを仕込み、混合・溶
解し、フラスコ内を窒素ガスで置換1−た後、撹拌振盪
しつつ60°Cの恒温水槽中に浸し、窒素気流下で30
分間重合させ、部分重合物を得た。続いて、この部分重
合物をガラスセル中に注入し、65°Cで5時間重合さ
せた後、100°Cで2時間重合させ、透明なシート状
の樹脂[A)を得た。得られた樹脂(A)を赤外線吸収
スペクトル(以下、I Rスペクトルと略ず)で分析し
たところ1710cm−’付近にイミド基の吸収、17
40cm−’付近にメタクリル酸メチルに基づくカルボ
ニル基の吸収が観測された。樹脂(A)のIRスペクト
ルを第3図に示す。Example 1 10 g of N-norbornylmethylmaleimide obtained in Synthesis Example 1, 90 g of methyl methacrylate, 084 g of lauroyl peroxide, and 0.2 g of lauroyl mercaptan were charged into a 500-piece Erlenmeyer flask equipped with a three-way stopcock, and mixed. After dissolving and purging the inside of the flask with nitrogen gas, it was immersed in a constant temperature water bath at 60°C with stirring and shaking, and heated for 30 minutes under a nitrogen stream.
Polymerization was carried out for a minute to obtain a partially polymerized product. Subsequently, this partially polymerized product was injected into a glass cell and polymerized at 65°C for 5 hours, and then at 100°C for 2 hours to obtain a transparent sheet-like resin [A]. When the obtained resin (A) was analyzed by infrared absorption spectrum (hereinafter abbreviated as IR spectrum), absorption of imide group at around 1710 cm-' was detected.
Absorption of carbonyl group based on methyl methacrylate was observed around 40 cm-'. The IR spectrum of resin (A) is shown in FIG.
実施例2
実施例1と同様の三角フラスコに合成例1で得られたN
−ノルボルニルメチルマレイミt”20g。Example 2 N obtained in Synthesis Example 1 was placed in the same Erlenmeyer flask as in Example 1.
-Norbornylmethylmaleimi t” 20g.
メタクリル酸メチル80g、過酸化ラウロイル0.4g
及びラウロ・イルメルカプタン0.2gを仕込み、実施
例1と全(同様に操作し、樹脂CB)を得た。樹脂CB
)の[Rスペクトルを第4図に示す。Methyl methacrylate 80g, lauroyl peroxide 0.4g
and 0.2 g of lauro il mercaptan were added to obtain resin CB in the same manner as in Example 1. resin CB
) [R spectrum is shown in FIG.
実施例3
実施例1と同様の三角フラスコに合成例2で得られたN
−ノルボルニルマレイミド10g1メタクリル酸メチル
90g、過酸化ラウロイル0.4g及びタウ1コイルメ
ルカプタン0.2gを仕込み、実施例1と全(同様に操
作し、樹脂(C)を得た。Example 3 N obtained in Synthesis Example 2 was placed in an Erlenmeyer flask similar to Example 1.
- 10 g of norbornylmaleimide, 90 g of methyl methacrylate, 0.4 g of lauroyl peroxide and 0.2 g of tau and 1 coil mercaptan were charged, and the same procedure as in Example 1 was carried out to obtain a resin (C).
樹脂〔C〕のIRスペクトルを第5図に示す。The IR spectrum of resin [C] is shown in FIG.
実施例4
実施例1と同様の三角フラスコに合成例2で得られたN
−ノルボルニルマレイミド20g、メタクリル酸メチル
80g、過酸化ラウロイル0.4g及びラウロイルメル
カプタン0.2 gを仕込み、実施例1と全く同様に操
作し、樹脂CD)を得た。Example 4 N obtained in Synthesis Example 2 was placed in an Erlenmeyer flask similar to Example 1.
- 20 g of norbornylmaleimide, 80 g of methyl methacrylate, 0.4 g of lauroyl peroxide and 0.2 g of lauroyl mercaptan were charged, and the same procedure as in Example 1 was carried out to obtain resin CD).
比較例1〜5
実施例1と同様の三角フラスコにN−フェニルマレイミ
ド(日本触媒化学工業■製、商品名イミレックスーP)
ヌはN−シクロへキシルマレイミド〔ブファル′ン・ラ
ント・パウアー(PFALTZ &BAtlER)社製
〕、メタクリル酸メチル、過酸化ラウロイル及びラウロ
イルメルカプタンを第1表に示す配合で仕込み、実施例
1と全く同様に操作し、樹脂(E)〜(1)を得た。Comparative Examples 1 to 5 N-phenylmaleimide (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name Imilex-P) was placed in the same Erlenmeyer flask as in Example 1.
N-cyclohexylmaleimide (manufactured by PFALTZ & BAtlER), methyl methacrylate, lauroyl peroxide and lauroyl mercaptan were prepared in the proportions shown in Table 1, and the mixture was exactly the same as in Example 1. Resins (E) to (1) were obtained.
以上のようにして得られた樹脂(A)〜〔1350gを
テトラヒドロフラン250gに)容解させた後、得られ
た溶液をメタノール2500g中に撹拌投入し、樹脂を
沈殿・析出させ、口利・乾燥し、白色粉末状の樹脂を得
た。この樹脂の重量平均分子l(Mw)と数平均分子量
(M、n)、ガラス転移温度及び熱分解温度を下記の方
法で測定し、結果を第2表に示す。After dissolving the resin (A) obtained as above (1,350 g in 250 g of tetrahydrofuran), the obtained solution was stirred and poured into 2,500 g of methanol to precipitate and precipitate the resin. A white powdery resin was obtained. The weight average molecular l (Mw), number average molecular weight (M, n), glass transition temperature and thermal decomposition temperature of this resin were measured by the following methods, and the results are shown in Table 2.
測淀、ji店
重量平均分子量(Mw)と数平均分子量(Mn)ゲルパ
ーミェーションクロマトグラフィー(GPC)を用いて
クロマトグラムを得、ポリスチレン換算することにより
求めた。Weight average molecular weight (Mw) and number average molecular weight (Mn) were obtained by obtaining a chromatogram using gel permeation chromatography (GPC) and converting it into polystyrene.
ガラス転移温度(Tg) 示差走査熱量計(DSC)で測定した。Glass transition temperature (Tg) It was measured with a differential scanning calorimeter (DSC).
熱分解温度(Td)
熱重量分析法により下記の条件で測定し、量%M量した
温度を読み取った。Thermal decomposition temperature (Td) Measured by thermogravimetric analysis under the following conditions, and the temperature measured in %M was read.
雰囲気 :空気20mR1分
昇温速度:5°C/分
5重
(以下余白)
上記の結果から明らかなとおり、本発明の実施例1〜4
で得られた樹脂は、N−フェニルマレイミドあるいはN
−シクロへキシルマレイミドとメタクリル酸メチルとの
共重合樹脂よりも耐熱性に優れている。Atmosphere: Air 20mR 1 minute Temperature rising rate: 5°C/min 5 times (blank below) As is clear from the above results, Examples 1 to 4 of the present invention
The resin obtained is N-phenylmaleimide or N
-It has better heat resistance than a copolymer resin of cyclohexylmaleimide and methyl methacrylate.
〔発明の効果]
本発明により得られる熱可塑性樹脂は、耐熱性及び透明
性に優れている。[Effects of the Invention] The thermoplastic resin obtained by the present invention has excellent heat resistance and transparency.
第1図は合成例1で得られたN −7/ルボルニルメチ
ルマレイミドの’ H−N M Rスペクトル、第2図
は合成例2で得られたN−ノルボルニルマレイミドの’
H−N M Rスペクトル、第3図は実施例Iで得ら
れた樹脂(A)のIRスペクトル、第4図は実施例2で
得られた樹脂CB)のIRスペクトル、第5図は実施例
3で得られた樹脂〔C]のIRスペク1−ルである。
代理人 弁理士 若 林 邦 彦Figure 1 shows the 'H-NMR spectrum of N-7/rubornylmethylmaleimide obtained in Synthesis Example 1, and Figure 2 shows the 'H-N MR spectrum of N-norbornylmaleimide obtained in Synthesis Example 2.
H-NMR spectrum, Figure 3 is the IR spectrum of resin (A) obtained in Example I, Figure 4 is the IR spectrum of resin CB) obtained in Example 2, and Figure 5 is the example. This is an IR spectrum 1 of resin [C] obtained in Step 3. Agent Patent Attorney Kunihiko Wakabayashi
Claims (1)
を示し、nは0又は1である〕で表わされるN−置換マ
レイミド及び (B)一般式〔II〕: ▲数式、化学式、表等があります▼〔II〕 〔式中R_1は水素原子又はメチル基を示し、R_2は
炭素原子数1〜5のアルキル基を示す〕で表わされる(
メタ)アクリル酸エステル を重合させることを特徴とする熱可塑性樹脂の製造法。 2、一般式〔 I 〕で表わされるN−置換マレイミドを
5〜60重量%使用する請求項1記載の熱可塑性樹脂の
製造法。[Claims] 1. (A) General formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is 0 or 1] and (B) general formula [II]: ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [II] [In the formula, R_1 represents a hydrogen atom or a methyl group , R_2 represents an alkyl group having 1 to 5 carbon atoms] (
A method for producing a thermoplastic resin, characterized by polymerizing a meth)acrylic acid ester. 2. The method for producing a thermoplastic resin according to claim 1, wherein 5 to 60% by weight of the N-substituted maleimide represented by the general formula [I] is used.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17840688A JPH0229405A (en) | 1988-07-18 | 1988-07-18 | Production of thermoplastic resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17840688A JPH0229405A (en) | 1988-07-18 | 1988-07-18 | Production of thermoplastic resin |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0229405A true JPH0229405A (en) | 1990-01-31 |
Family
ID=16047938
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17840688A Pending JPH0229405A (en) | 1988-07-18 | 1988-07-18 | Production of thermoplastic resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0229405A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6946523B2 (en) * | 2001-02-07 | 2005-09-20 | Henkel Corporation | Heterobifunctional monomers and uses therefor |
WO2014061149A1 (en) * | 2012-10-19 | 2014-04-24 | 旭化成ケミカルズ株式会社 | Methacrylic resin-containing cover for vehicle members |
-
1988
- 1988-07-18 JP JP17840688A patent/JPH0229405A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6946523B2 (en) * | 2001-02-07 | 2005-09-20 | Henkel Corporation | Heterobifunctional monomers and uses therefor |
WO2014061149A1 (en) * | 2012-10-19 | 2014-04-24 | 旭化成ケミカルズ株式会社 | Methacrylic resin-containing cover for vehicle members |
CN104736373A (en) * | 2012-10-19 | 2015-06-24 | 旭化成化学株式会社 | Methacrylic resin-containing cover for vehicle members |
US9920148B2 (en) | 2012-10-19 | 2018-03-20 | Asahi Kasei Chemicals Corporation | Vehicle part cover including methacrylic-based resin |
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