CN105601772B - The method that one step prepares crosslinked polystyrene or cross-linked copolymer - Google Patents
The method that one step prepares crosslinked polystyrene or cross-linked copolymer Download PDFInfo
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- CN105601772B CN105601772B CN201610090146.9A CN201610090146A CN105601772B CN 105601772 B CN105601772 B CN 105601772B CN 201610090146 A CN201610090146 A CN 201610090146A CN 105601772 B CN105601772 B CN 105601772B
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- polybromide
- degree
- methyl
- functionality
- crosslinked polystyrene
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 32
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229920001577 copolymer Polymers 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 150000003384 small molecules Chemical class 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 16
- 229920000768 polyamine Polymers 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- GHPHCDZRWUIBCE-UHFFFAOYSA-N 3-bromo-2-methylpropanoyl bromide Chemical class BrCC(C)C(Br)=O GHPHCDZRWUIBCE-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 235000021050 feed intake Nutrition 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- RIBFXMJCUYXJDZ-UHFFFAOYSA-N propanoyl bromide Chemical compound CCC(Br)=O RIBFXMJCUYXJDZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- ICNCZFQYZKPYMS-UHFFFAOYSA-N 2-methylpropanoyl bromide Chemical compound CC(C)C(Br)=O ICNCZFQYZKPYMS-UHFFFAOYSA-N 0.000 claims 1
- 238000007445 Chromatographic isolation Methods 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- NZLYXIUDQUBQGU-UHFFFAOYSA-N benzene-1,2,4,5-tetramine;hydrochloride Chemical class Cl.NC1=CC(N)=C(N)C=C1N NZLYXIUDQUBQGU-UHFFFAOYSA-N 0.000 claims 1
- 238000011097 chromatography purification Methods 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 229920006037 cross link polymer Polymers 0.000 abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 38
- 238000004132 cross linking Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- -1 nitrogen-oxygen free radical Chemical class 0.000 description 8
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001723 carbon free-radicals Chemical class 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JPMRGPPMXHGKRO-UHFFFAOYSA-N 2-(chloromethyl)pyridine hydrochloride Chemical class Cl.ClCC1=CC=CC=N1 JPMRGPPMXHGKRO-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ZPHQBFRCXUIIAZ-UHFFFAOYSA-N benzene;hydrochloride Chemical compound Cl.C1=CC=CC=C1 ZPHQBFRCXUIIAZ-UHFFFAOYSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- FQFILJKFZCVHNH-UHFFFAOYSA-N tert-butyl n-[3-[(5-bromo-2-chloropyrimidin-4-yl)amino]propyl]carbamate Chemical compound CC(C)(C)OC(=O)NCCCNC1=NC(Cl)=NC=C1Br FQFILJKFZCVHNH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to cross-linked polymer preparation field, it is desirable to provide a kind of method that a step prepares crosslinked polystyrene or cross-linked copolymer.This method includes：After taking small molecule polybromide, styrene monomer, polyamine ligand and solvent reaction deoxidation, copper powder is added under nitrogen protection；Reaction is made branch point and is distributed measurable crosslinked polystyrene；Or small molecule polybromide is substituted as initiator using the brominated multi-arm polyethylene glycol oxide of end group or other macromolecular polybromides, branch point is made under the same reaction conditions and is distributed measurable cross-linked copolymer.The synthesis condition of the present invention is simple, and polybromide synthesis is convenient, structurally variable；Di-vinyl monomers need not be added as crosslinking agent；The reactivity of product is high, method is easy, preparation condition is gentle；And there is degradable branch point, by varying the species of macromolecular polybromide, the crosslinked polystyrene of different functionalities can be prepared.With abundant potential using value.
Description
Technical field
The present invention is to prepare crosslinked polystyrene or copolymerzation with cross-linking on cross-linked polymer preparation field, more particularly to a step
The method of thing.
Background technology
Condensation polymerization or vinyl monomer containing polyfunctional monomer can be handed over the copolymerization of a small amount of di-vinyl monomers
Linked polymer.For linear polymer, cross-linked polymer has a tridimensional network, its mechanical property, heat endurance,
Wearability, solvent resistance and creep resistant property have significant difference, thus in thermosets, binding agent, drug controlled release
There is important application Deng field.
The structure of cross-linked polymer has a major impact its performance.The main crosslinking degree of description for cross-linked structure (or
Crosslink density), crosslinking points distribution and end chain (also known as suspended chain) content etc. (Polymer Physics .2001, publishing house of Fudan University).
The degree of cross linking refers to the average molecular weight of the chain (also referred to as network chain) between two crosslinking points；Crosslink density refers to the knot shared by crosslinking points
Structure unit divides rate.The methods of the two parameters can be by gravimetric method, dynamic mechanical analysis, positron annihilation or nuclear magnetic resonance method
Characterization.(Macromolecules,2008.41(15):5729-5743.；1995.28(26):8840-8844.；2008.41
(13):4850-4855.；Langmuir,2008.24(9):4470-4472.；Journal of Chemical Physics,
1943.11(11):521-526.；Polymer,2005.46(3):661-669.) their physical properties to cross-linked polymer have
Important influence.Current correlative study is all (or to hand over the mechanical property of cross-linking system, such as viscosity, modulus etc. and the degree of cross linking
Join density) it is associated.The molecular weight distribution of network chain, can describe the uniformity of crosslinking points distribution, but there is no effective table at present
Sign method.Hot hole method (thermoporosimetry or thermoporometry) (Thermochimica Acta,
1977.21(1):59-88.；2005.433(1-2):27-50.；Polymer Degradation and Stability,
1999.63(1):121-126.；Polymer Degradation and Stability,1999.65(3):415-420.) may be used
For characterizing the pore-size distribution of high-molecular gel, molecular weight and the distribution of network chain can be extrapolated by pore-size distribution.In addition,
End chain with free end group also has a major impact the property of cross-linking system, particularly there is weight to its mechanics and chemical reactivity
Influence.(Macromolecules,2001.34(13):4591-4596.；Polymer,2009.50(2):347-356.)
Free radical coupling reaction is used for Macroscopic single crystal by existing document report.α-bromine under the research different condition such as Fukuda
For the atom transferred free radical coupling reaction (ATRC) of polystyrene (PS-Br).(e-Polymers 2002,13),
Matyjaszewski etc. report using Nanometer Copper, iron simple substance Fe (0), stannous octoate (SnOct2) and ascorbic acid etc. as
The ATRC reactions of reducing agent research PS-Br.(Macromolecules 2004,37,3120-3127.) Monteiro etc. have studied
Cross-coupling reaction between macromolecular radical and the macromolecular for containing stable nitrogen-oxygen free radical (such as TEMPO).The intersection is even
Close reaction efficiency it is very high (>99%), generation is very low from the ratio of coupling reaction between carbon radicals, can almost ignore
Disregard.(Journal of Polymer Science Part A:Polymer Chemistry 2010,48,2214-2223.)
The reports such as Yagci prepare Parylene to dibromo paraxylene is used as monomer, by free radical coupling reaction, but to polymerization
Thing does not carry out detailed characterization (Designed Monomers and Polymerization, 2007,10,575).Although
There is relevant report to prepare polymer using free radical coupling reaction, but cross-linked polymeric is prepared using carbon radicals coupling reaction
The example of thing is rarely reported.
Crosslinked polystyrene is the precursor of many exchanger resins, is had a wide range of applications, and is such as used for ion exchange resin, is coagulated
Glue chromatography etc..Crosslinked polystyrene synthetic method main at present is to be copolymerized styrene and a small amount of divinylbenzene, is obtained
Crosslinking points distribution in polymer is random and non-uniform.Do not melted since the polymer of gained is insoluble, existing table can not be passed through
Sign means directly obtain the structural information of polymer, and the distribution of its crosslinking points is also unknown.
The content of the invention
The technical problem to be solved in the present invention is overcome deficiency of the prior art, there is provided it is poly- that an a kind of step prepares crosslinking
The method of styrene or cross-linked copolymer.
To solve technical problem, solution of the invention is：
A kind of method that a step prepares crosslinked polystyrene or cross-linked copolymer is provided, it is concretely comprised the following steps：
1 part of small molecule polybromide is taken as initiator, 10F2~200F2The styrene monomer, 0.7F of part2~10F2
The polyamine ligand of part is added in reactor, is added appropriate solvent and make it that initiator concentration is 0.05mol/L~0.4mol/L；
After deoxidation, 0.7F is added under nitrogen protection2~10F2The copper powder of part；Then 12 minutes~700 points are reacted at 20~70 DEG C
Clock, that is, be made branch point and be distributed measurable crosslinked polystyrene；
Wherein, the number to feed intake is molfraction；Wherein F2For the degree of functionality of small molecule polybromide, and F2For 3~6；
Alternatively, the more brominations of small molecule are substituted with the brominated multi-arm polyethylene glycol oxide of end group or other macromolecular polybromides
Compound is made branch point and is distributed measurable cross-linked copolymer under the same reaction conditions as initiator；Wherein, end group bromine
The degree of functionality of the multi-arm polyethylene glycol oxide of change is F3, and F3For 3~8；The degree of functionality of other macromolecular polybromides is F4, and
F4For 3~6；
The polyamine ligand is：2,2 '-bipyridyl, 4,4 '-two (5- nonyls) -2,2 '-bipyridyls, N, N, N ', N ",
N "-pentamethyldiethylenetriamine, 1,1,4,7,10,10- hexamethyl triethylene tetramines, three [2- (dimethylamino) ethyl] amine, three
[(2- pyridine radicals) methyl] amine or N, N, N ', any one in N '-four [(2- pyridine radicals) methyl] -1,2- ethylenediamines；
The solvent is：Tetrahydrofuran, 2- methyltetrahydrofurans, 1-methyl-2-pyrrolidinone, N,N-dimethylformamide, two
Any one in methyl sulfoxide or methyl phenyl ethers anisole.
In the present invention, the chain hop count that the branch point of the crosslinked polystyrene is connected is between 3~6, the crosslinking
The chain hop count that the branch point of copolymer is connected between 3~8, and can acid or alkali catalysis under, in the swollen state with
Exchange reaction occurs at branch point for monohydric alcohol or monoamine, and the line polymer that degraded obtains dissolving in solvent (is defined as solving
Crosslinking, by the characterization to solving cross-linking products, can measure the branch point distribution situation of crosslinked polystyrene and cross-linked copolymer).
In the present invention, network chain (segment for connecting two branch points) degree of polymerization of the crosslinked polystyrene is 8~200
Between, and the degree of polymerization of network chain is sized to be regulated and controled by adding monomer number and polymerization time.
In the present invention, the polybromide as initiator is prepared by following methods：
(1) preparation of small molecule polybromide
It is F by 1 part of degree of functionality1Polyalcohol or polyamine, F1Part triethylamine is dissolved in anhydrous tetrahydro furan, cold in ice bath
It is lower that 1.1F is added dropwise1Part bromacyl bromide, is stirred overnight when small (18), then by reaction product through recrystallization or column chromatography at room temperature
Isolate and purify, that is, obtain small molecule polybromide, its degree of functionality is F2, and F2=F1；
(2) preparation of the brominated multi-arm polyethylene glycol oxide of end group
It is F by 1 part of degree of functionality3Multi-arm polyethylene glycol oxide, F3Part triethylamine is dissolved in anhydrous tetrahydro furan, cold in ice bath
It is lower that 1.1F is added dropwise3Part bromo- 2- methyl propionyl bromides of 2-, are stirred overnight when small (16), reaction product is through cold n-hexane at room temperature
Or after ether deposition and purification, that is, the brominated multi-arm polyethylene glycol oxide of end group is obtained, and its degree of functionality is F3, F3For 3~8；Wherein,
The number to feed intake is molfraction；
(3) preparation of other macromolecular polybromides
It is F to take degree of functionality made from 1 part of step (1)1Polybromide, 10F1~200F1Part monomer, 0.1F1Part is polynary
Amine ligand is added in reactor, adds the THF of volume fraction 25% as solvent；After deoxidation, 0.1F is added under nitrogen protection1
Part cuprous bromide；When reaction 1 is small at 60 DEG C, macromolecular polybromide is obtained after purification, its degree of functionality is F4, and F4=
F1；Wherein, the number to feed intake is molfraction；The monomer is methyl acrylate, methyl methacrylate or the tertiary fourth of acrylic acid
Ester.
In the present invention, the polyalcohol or polyamine refer to the compound containing multiple hydroxyls or amino, and F1For 3~6,
Any one specially in trimethylolpropane, phloroglucin, 1,2,4,5- tetraminos benzene hydrochloride or bipentaerythrite；
In the present invention, the bromacyl bromide is 2- bromos propionyl bromide or the bromo- 2- methyl propionyl bromides of 2-.
The realization principle of the present invention：
Small molecule polybromide is being used as initiator under copper/ligand effect, generates free radicals initiation vinyl monomer
Increased.Phase after the reaction, using the spontaneous coupling reaction of vinyl monomer, a step prepares crosslinked polystyrene；Same batten
, can step preparation friendship using the brominated multi-arm polystyrene of end group or other macromolecular polybromides as initiator under part
Ally the communists polymers.
Due to having ester group or amide groups at branch point, under the catalysis of acid or alkali, crosslinked polystyrene or copolymerzation with cross-linking
In the state of swelling with monohydric alcohol or amine exchange reaction can occur for thing, obtain dissolving in the line polymer of solvent.We
The cross-linked polymer of this kind of generation degradation reaction at crosslinking points is defined as that crosslinked polymer can be solved.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, synthesis condition of the invention is simple, and polybromide synthesis is convenient, structurally variable；
2nd, di-vinyl monomers need not be added as crosslinking agent, only with monovinyl compound styrene as monomer,
Utilize carbon radicals coupling reaction, you can crosslinked polystyrene or cross-linked copolymer is prepared in a step；
3rd, the reactivity height of the invention for preparing crosslinked polystyrene and cross-linked copolymer, method simplicity, preparation condition temperature
With；And there is degradable branch point, crosslinked polystyrene can be degraded into line polymer at branch point by reacting
To characterize its branch point distribution situation；
4th, the species of the invention by varying macromolecular polybromide, can prepare the crosslinking polyphenyl second of different functionalities
Alkene.The brominated more polyethylene glycol oxides of end group are such as used, the crosslinking that can prepare amphipathic (can be swollen in water phase and oil phase) is total to
Polymers；Using the brominated multi-arm polyacrylic acid tert-butyl ester of end group, gel oleophylic and hydrophilic journey can be adjusted by hydrolysis degree
Degree；Using the poly- N-isopropylacrylamide of the brominated multi-arm of end group, the cross-linked polymer of Thermo-sensitive can be prepared.With abundant
Potential using value.
Embodiment
The present invention is described in further detail with reference to embodiment：
The present invention is more fully understood in the professional technician that the following examples can make this professional, but not with any side
The formula limitation present invention.In the following embodiments, all polymerisations carry out under the anhydrous reaction condition of anaerobic.
It is as follows for the small molecule polybromide molecular formula in embodiment：
It is as follows for the abbreviation in embodiment：
THF：Tetrahydrofuran；Me-THF：2- methyltetrahydrofurans；NMP：1-methyl-2-pyrrolidinone；DMF：N, N- dimethyl
Formamide；DMSO：Dimethyl sulfoxide (DMSO)；Anisole：Methyl phenyl ethers anisole；DCM：Dichloromethane；MA：Methyl acrylate；MMA：Metering system
Sour methyl esters；tBA：Tert-butyl acrylate；BPY:2,2 '-bipyridyl；DNBPY：4,4 '-two (5- nonyls) -2,2 '-bipyridyls；
PMDETA：N, N, N ', N ", N "-pentamethyldiethylenetriamine；HMTETA：1,1,4,7,10,10- hexamethyl trientines；
Me6-TREN：Three [2- (dimethylamino) ethyl] amine；TPMA：Three [(2- pyridine radicals) methyl] amine；TPEN：N, N, N ', N '-four
[(2- pyridine radicals) methyl] -1,2- ethylenediamines.
The synthesis of 1 polyamine ligand TPMA of embodiment
16.4g 2- chloromethyl pyridine hydrochlorides (0.1mol) are dissolved in 40mL deionized waters, ice bath cooling, slowly adds
Enter dissolved with 0.1mol sodium hydroxide 20mL aqueous solutions, solution is changed into pink.Add 80mL and contain 5.4g2- (aminomethyl) pyridine
The DCM solution of (0.05mol), is warmed to room temperature.Added with microsyringe dissolved with 0.1mol sodium hydroxide 20mL aqueous solutions, 50 is small
When drip off.Stopping reaction, organic phase is washed with 3 × 10mL 15%NaOH aqueous solutions, merge organic phase, anhydrous magnesium sulfate is dried,
Filtering, concentration.Product is extracted under fluidized state with ether, removes insoluble matter, cooling, product crystallizes in ether, filters.After
Continuous recrystallize 3 times obtains faint yellow acicular crystal, yield 37%.1H NMR(400MHz,CDCl3):8.54-8.53(d,3H),
7.67-7.64 (t, 3H), 7.60-7.58 (d, 3H), 7.16-7.13 (t, 3H), 3.89 (s, 6H, CH2-N).Elemental analysis：Survey
Value (theoretical value):C,74.38(74.46)；H,6.29(6.25).
The synthesis of 2 polyamine ligand TPEN of embodiment
13.12g 2- chloromethyl pyridine hydrochlorides (0.08mol) are dissolved in 30mL deionized waters, ice bath cooling, slowly
Add dissolved with 0.08mol sodium hydroxide 15mL aqueous solutions, solution is changed into pink.Add 60mL and contain 1.2g ethylenediamines
The DCM solution of (0.02mol), is warmed to room temperature.Added with microsyringe dissolved with 0.08mol sodium hydroxide 15mL aqueous solutions, 50
Hour drips off.Stop reaction, wash organic phase with 3 × 10mL 15%NaOH aqueous solutions, merge organic phase, anhydrous magnesium sulfate is done
It is dry, filter, concentration.Product is extracted under fluidized state with ether, removes insoluble matter, cooling, product crystallizes in ether, mistake
Filter.Continue to recrystallize 3 times and obtain faint yellow acicular crystal, yield 37%.1H NMR(400MHz,CDCl3):8.46-8.50(d,
4H),7.56-7.59(t,4H),7.44-7.48(d,4H),7.08-7.13(t,4H),3.78(s,8H,C-CH2-N),2.77
(s,4H,N-CH2-CH2-N).Elemental analysis：Measured value (theoretical value):C,73.48(73.56)；H,6.67(6.65).
The synthesis of 3 small molecule polybromide 3a of embodiment
By 2.7g 1,1,1- trimethylol-propanes (2 × 10-2Mol), 8mL triethylamines (6 × 10-2Mol), 50mL DCM
Mixing, is placed in 250mL three-necked flasks, ice bath cooling.The bromo- 2- methyl propionyl bromides (6.6 × 10 of 8.2mL 2- will be contained-2mol)
DCM solution (50mL) instill dropwise in three-necked flask, 1 drips off when small, white precipitate occurs, is warming up to room temperature (25 DEG C), mistake
When night stirring 18 is small.Filtering, filtrate are washed three times with 50mL 1mol/L HCl solutions, saturation NaHCO3Aqueous solution washs three times,
50mL deionized waters are washed three times, and 50mL saturations NaCl washed once, anhydrous MgSO4It is dried overnight.Filtering, after concentration, obtains
Yellow viscous liquid.Crude product with methanol recrystallizes twice, is dried in vacuum overnight after filtering at 40 DEG C, obtains white crystal.1H NMR(400MHz,CDCl3)δ(ppm):4.19(6H,s,CH2- O-C=O), 1.94 (18H, s, O=C-C (CH3)2-),
1.60-1.67(2H,q,CH3-CH2-),0.82-0.97(3H,t,CH3-CH2-).Elemental analysis：Measured value (theoretical value):C,
37.09(37.20)；H,5.05(5.03).
The synthesis of 4 small molecule polybromide 3b of embodiment
The bromo- 2- methyl propionyl bromides of 2- in embodiment 3 are changed to 7mL 2- bromos propionyl bromide (6.6 × 10-2Mol), remaining
Operating procedure is the same as embodiment 3.Obtain white crystal.1H NMR(400MHz,CDCl3)δ(ppm):4.68-4.73 (3H, q, O=C-
CH-),3.94(6H,s,CH2- O-C=O), 1.91-1.97 (9H, d, O=C-CH (CH3)-),1.63-1.73(2H,q,CH3-
CH2-),0.84-0.95(3H,t,CH3-CH2-).Elemental analysis：Measured value (theoretical value):C,33.29(33.42)；H,4.31
(4.30)。
The synthesis of 5 small molecule polybromide 3c of embodiment
Trihydroxylic alcohol in embodiment 1 is changed to 2.52g phloroglucins (2 × 10-3Mol), the same embodiment of remaining operating procedure
3.Crude product with methanol recrystallizes three times, is dried in vacuum overnight after filtering at 40 DEG C, obtains white crystal.1H NMR
(400MHz,CDCl3)δ(ppm):6.97 (18H, s, O=C-C (CH3)2-),2.06(3H,s,C-CH-C).Elemental analysis：Measurement
It is worth (theoretical value):C,37.52(37.73)；H,3.72(3.69).
The synthesis of 6 small molecule polybromide 4a of embodiment
By 5.68g 1,2,4,5- tetraminos benzene hydrochloride (2 × 10-2Mol), 10.5mL triethylamines (8 × 10-2Mol),
50mL DCM are mixed, and are placed in 250mL three-necked flasks, ice bath cooling.11mL 2- methyl -2- bromos propionyl bromide (8.8 will be contained
×10-2Mol DCM solution (50mL)) is instilled in three-necked flask dropwise, and 1 drips off when small, white precipitate occurs, is warming up to room temperature
(25 DEG C), are stirred overnight.Post-processing step is the same as embodiment 3.Obtain white crystal.1H NMR(400MHz,CDCl3)δ(ppm):
8.01 (2H, s, C-CH-C), 2.07 (24H, s, O=C-C (CH3)2-).Elemental analysis：Measured value (theoretical value):C,35.32
(35.99)；H,4.14(4.12)；N,7.61(7.63).
The synthesis of 7 small molecule polybromide 6a of embodiment
By 5.41g bipentaerythrites (2 × 10-2Mol), 17mL triethylamines (12 × 10-2Mol), 50mL DCM are mixed, and are put
In 250mL three-necked flasks, ice bath cooling.16.5mL 2- methyl -2- bromos propionyl bromide (13.2 × 10 will be contained-2Mol)
DCM solution (50mL) is instilled in three-necked flask dropwise, and 1 drips off when small, white precipitate occurs, is warming up to room temperature (25 DEG C), stirring
Overnight.Post-processing step is the same as embodiment 3.Obtain white crystal.Obtain white crystal.1H NMR(400MHz,CDCl3)δ(ppm):
3.94(12H,s,CH2- O-C=O), 3.77 (4H, s, CH2-O-CH2-), 1.97 (36H, s, O=C-C (CH3)2-).Element point
Analysis：Measured value (theoretical value):C,34.40(35.57)；H,4.61(4.57).
The preparation of the brominated three arms polyethylene glycol oxide TPEO1 of 8 end group of embodiment
The THF mixing of 5.0g tri- arm PEG (1000g/mol, 5mmol), 2.3mL (16.5mmol) TEA, 20mL dryings, puts
In 150mL there-necked flasks, nitrogen protection, ice bath cooling.It is slowly added dropwise containing the bromo- 2- methyl propionyl of 2.1mL (16.5mmol) 2-
The THF solution of the 20mL dryings of bromine, gradually appears white precipitate, 1h is dripped off.Stir at room temperature, when reaction overnight 16 is small.
Filtering, is spin-dried for solvent, adds 50mL DCM and is dissolved.Dilute hydrochloric acid, the saturation NaHCO of 1M is used respectively3Aqueous solution
And deionized water washing is washed three times, then with saturation NaCl, obtains light yellow color settled solution, appropriate anhydrous MgSO is added4
It is dry.
Filtering, is dissolved with a small amount of anhydrous ether after concentration, is slowly added dropwise in cold n-hexane and precipitates.After precipitating twice,
40 DEG C of vacuum drying ovens are put into be dried overnight.Obtain yellow viscous liquid.1H NMR(400MHz,CDCl3)δ(ppm):4.32(6H,
s,CH2- O-C=O), 3.64 (83H, m, CH2-O-CH2-), 1.94 (18H, s, O=C-C (CH3)2-)。
The preparation of the brominated multi-arm polyethylene glycol oxide of end group of embodiment 9-17 different molecular weights
When operated according to feeding intake for embodiment 8, synthesize the multi-arm polyethylene glycol oxide of different molecular weight.
The degree of functionality F of raw material TPEO1-TPEO43For 3, the degree of functionality F of raw material QPEO1-TPEO33For 4, raw material OPEO1-
The degree of functionality F of OPEO33For 8；
The triethylamine number added in embodiment 8~11 is 1.1 × 3；The triethylamine number added in embodiment 12-14 is
1.1 × 4, the triethylamine number added in embodiment 15-17 is 1.1 × 8；
The bromo- 2- methyl propionyl bromide numbers of 2- added in embodiment 8~11 are 1.1 × 3；Added in embodiment 12-14
The bromo- 2- methyl propionyl bromide numbers of 2- be the bromo- 2- methyl propionyl bromide numbers of the 2- added in 1.1 × 4, embodiment 15-17 be 1.1 ×
8；
Specific preparation condition and the results are shown in Table 1.
The preparation condition and result of the 1 brominated multi-arm polyethylene glycol oxide of embodiment 8-17 middle-end bases of table*
Reaction condition：Rate of charge：[raw material]:[triethylamine]:[the bromo- 2- methyl-propionyl bromides of 2-]=1:1.1F:1.1F；Instead
Between seasonable：16 it is small when.
The preparation of 18 macromolecular terbromide TPMA1 of embodiment
By 1.06g small molecule polybromides 3a (2 × 10-3Mol), 125 μ L PMDETA (6 × 10-4mol)、5.4mL
MA(6×10-2Mol) and 5mL THF are added in Schlenk bottles of 20mL pyriforms.Liquid nitrogen frozen-vacuum-melting circulation deoxygenation three times
Afterwards, 86.1mg cuprous bromides (6 × 10 are added under nitrogen protection-4mol).At 60 DEG C, when reaction 1 is small, liquid nitrogen quenching terminates anti-
Should.Polymer is dissolved in DCM, and column copper removal is crossed through neutral alumina, concentration.With methanol extraction, filtering, 40 DEG C were dried in vacuo
At night, obtain white powdery solids.Resulting polymers are tested through gel permeation chromatography (GPC)：Number-average molecular weight (Mn)=
2250g/mol, molecular weight distributing index (PDI)=1.09.
The preparation of other macromolecular polybromides of embodiment 19-20
According to the operation of embodiment 18, use MMA or tBA instead and synthesize other macromolecular polybromides as monomer；
The THF of volume fraction 25% is added as solvent；
Specific preparation condition and the results are shown in Table 2；
The preparation condition and result of macromolecular polybromide in 2 embodiment 18-20 of table*
*Reaction condition：Initiator：Small molecule polybromide 3a；Ligand：PMDETA；Rate of charge：[initiator]:[bromination
It is cuprous]:[ligand]:[monomer]=1:0.3:0.3:30；Solvent：THF；Temperature：60℃.
21 one-step method of embodiment prepares crosslinked polystyrene
116mg small molecule polybromides 3a (3 × 10-4Mol), 188 μ L PMDETA (9 × 10-4Mol), 1mL styrene
(9×10-3Mol) and 1.8mL THF are added in Schlenk bottles of 10mL straights, initiator concentration 0.1mol/L.Liquid nitrogen frozen-
Vacuum-melting circulation after deoxygenation, adds 57.1mg Cu powder (9 × 10 under nitrogen protection three times-4mol).At 40 DEG C, reaction 240
Minute obtain g., jelly-like solid, the reaction was continued 1 it is small when after liquid nitrogen quenching terminate reaction.Extracted 3 times at 60 DEG C with 10mL DMF,
40 DEG C be dried in vacuum overnight after obtain faint yellow flexible solid globules.
One-step method prepares crosslinked polystyrene under the conditions of embodiment 22-43 differential responses
According to the operation of embodiment 21, it is prepared for using different monomers concentration, different solvents, different temperatures, different ligands
A series of cross-linked polymers, specific reaction condition and the results are shown in Table 3.
PMDETA, DNBPY, BPY, HMTETA, Me has been respectively adopted in wherein embodiment 21-276- TREN, TPMA or
Polyamine ligands different TPEN；
Different molten of THF, Me-THF, NMP, DMF, DMSO or Anisole has been respectively adopted in embodiment 23 and 28-32
Agent；
Embodiment 23 and 33-37 have been separately added into 1 × 3,0.7 × 3,0.8 × 3,2 × 3,5 × 3 or 10 × 3 part of copper
Powder；
20,40 or 70 DEG C of reaction temperature has been respectively adopted in embodiment 23,42-43；
It is equal with copper powder to add number for ligand in each embodiment；
Specific preparation condition and the results are shown in Table 3
The preparation condition and result of crosslinked polystyrene are prepared in 3 embodiment 20-43 of table under the conditions of differential responses
*Reaction condition：Initiator：Small molecule polybromide 3a；Rate of charge：[initiator]:[monomer]=1:30.
The preparation of the different crosslinked polystyrene of chain length between embodiment 44-48 branch points
According to the operation of embodiment 21, using different monomeric charge ratios, the different friendship of chain length between synthesizing branched point
Linked polymer.
Embodiment 44-48 has been separately added into 10 × 3,20 × 3,43.3 × 3,100 × 3 or 200 × 3 parts of copper powder；
Specific reaction condition and the results are shown in Table 4.
In 4 embodiment 44-48 of table between branch point the different crosslinked polystyrene of chain length preparation condition and result
*Reaction condition：Initiator：Small molecule polybromide 3a；Ligand：PMDETA；Rate of charge：[initiator]:[copper]:
[ligand]=1:3:3；Initiator concentration：0.1mol/L；Temperature：40℃；Solvent：THF.
The preparation of the crosslinked polystyrene or cross-linked copolymer of embodiment 49-66 difference branching units
According to the operation of embodiment 21, crosslinking polyphenyl second is prepared using small molecule polybromide 3a, 3b, 3c, 4a, 6a
Alkene, macromolecular polybromide TPEO1-TPEO4, QPEO1-QPEO3, OPEO1-OPEO3, TPMA1, TPMMA1, TptBA1 system
Standby cross-linked copolymer.Specific reaction condition and the results are shown in Table 5.
The different cross-linked polymers of branching unit or the preparation condition of cross-linked copolymer and result in 5 embodiment 49-66 of table*
Reaction condition：Rate of charge：[copper]:[ligand]=1:1；Initiator concentration：0.1mol/L；Ligand：PMDETA；Temperature
Degree：40℃；Solvent：THF.
The solution of 67 crosslinked polystyrene of embodiment or cross-linked copolymer is crosslinked
Crosslinked polystyrene or cross-linked copolymer sample (50mg-200mg) are added in 100mL flasks with 30mL THF,
Swelling is stirred at 60 DEG C.After 30 minutes, in four batches, every 30 minutes, it is added dropwise dissolved with 0.02mol highly basic (potassium hydroxide or hydrogen
Sodium oxide molybdena) or strong acid (sulfuric acid or p-methyl benzenesulfonic acid) methanol or n-butylamine solution 20mL.The reaction was continued 24 it is small when after by solvent
It is spin-dried for, with CH2Cl2/H2O systems extract, and collect oil phase, then be washed with deionized water to neutrality.Solvent is spin-dried for, obtains solving crosslinked
Line polymer sample.
Finally it should be noted that listed above is only specific embodiment of the invention.It is clear that the invention is not restricted to
Above example, can also there is many variations.Those of ordinary skill in the art can directly lead from present disclosure
All deformations for going out or associating, are considered as protection scope of the present invention.
Claims (5)
1. a kind of method that a step prepares crosslinked polystyrene or cross-linked copolymer, it is characterised in that it is concretely comprised the following steps：
1 part of small molecule polybromide is taken as initiator, 10F2~200F2The styrene monomer, 0.7F of part2~10F2Part it is more
First amine ligand is added in reactor, is added appropriate solvent and make it that initiator concentration is 0.05mol/L~0.4mol/L；Deoxidation
Afterwards, 0.7F is added under nitrogen protection2~10F2The copper powder of part；Then 12 minutes~700 minutes are reacted at 20~70 DEG C, i.e.,
Branch point is made and is distributed measurable crosslinked polystyrene；
Wherein, the number to feed intake is molfraction；Wherein F2For the degree of functionality of small molecule polybromide, and F2For 3~6；
Alternatively, small molecule polybromide is substituted with the brominated multi-arm polyethylene glycol oxide of end group or other macromolecular polybromides
As initiator, branch point is made under the same reaction conditions and is distributed measurable cross-linked copolymer；Wherein, end group is brominated
The degree of functionality of multi-arm polyethylene glycol oxide is F3, and F3For 3~8；The degree of functionality of other macromolecular polybromides is F4, and F4For 3
~6；
The polyamine ligand is：2,2 '-bipyridyl, 4,4 '-two (5- nonyls) -2,2 '-bipyridyls, N, N, N ', N ", N "-five
Methyl diethyl triamine, 1,1,4,7,10,10- hexamethyl triethylene tetramines, three [2- (dimethylamino) ethyl] amine, three [(2- pyrroles
Piperidinyl) methyl] amine or N, N, N ', any one in N '-four [(2- pyridine radicals) methyl] -1,2- ethylenediamines；
The solvent is：Tetrahydrofuran, 2- methyltetrahydrofurans, 1-methyl-2-pyrrolidinone, N,N-dimethylformamide, dimethyl
Any one in sulfoxide or methyl phenyl ethers anisole；
The chain hop count that the branch point of the crosslinked polystyrene is connected is between 3~6, the branch point of the cross-linked copolymer
The chain hop count connected between 3~8, and can acid or alkali catalysis under, in the swollen state with monohydric alcohol or monoamine
Exchange reaction occurs at branch point, degraded obtains dissolving in the line polymer of solvent.
2. method according to claim 1, it is characterised in that the network chain degree of polymerization of the crosslinked polystyrene 8~200 it
Between, and the degree of polymerization of network chain is sized to be regulated and controled by adding monomer number and polymerization time.
3. method according to claim 1, it is characterised in that the polybromide as initiator passes through following methods
Prepare：
(1) preparation of small molecule polybromide
It is F by 1 part of degree of functionality1Polyalcohol or polyamine, F1Part triethylamine is dissolved in anhydrous tetrahydro furan, under ice cooling, 4
1.1F is added dropwise1Part bromacyl bromide, is stirred overnight at room temperature, then by reaction product through recrystallization or column chromatographic isolation and purification, i.e.,
Small molecule polybromide is obtained, its degree of functionality is F2, and F2=F1；The number that feeds intake of each reaction raw materials is molfraction；
(2) preparation of the brominated multi-arm polyethylene glycol oxide of end group
It is F by 1 part of degree of functionality3Multi-arm polyethylene glycol oxide, F3Part triethylamine is dissolved in anhydrous tetrahydro furan, under ice cooling, 4
1.1F is added dropwise3Part bromo- 2- methyl propionyl bromides of 2-, are stirred overnight at room temperature, and reaction product is pure through cold n-hexane or ether precipitation
After change, that is, the brominated multi-arm polyethylene glycol oxide of end group is obtained, and its degree of functionality is F3, F3For 3~8；Wherein, the number to feed intake is
Molfraction；
(3) preparation of other macromolecular polybromides
It is F to take degree of functionality made from 1 part of step (1)1Polybromide, 10F1~200F1Part monomer, 0.1F1Part polyamine is matched somebody with somebody
Body is added in reactor, adds the THF of volume fraction 25% as solvent；After deoxidation, 0.1F is added under nitrogen protection1Part bromine
Change cuprous；When reaction 1 is small at 60 DEG C, macromolecular polybromide is obtained after purification, its degree of functionality is F4, and F4=F1；Its
In, the number to feed intake is molfraction；The monomer is methyl acrylate, methyl methacrylate or tert-butyl acrylate.
4. method according to claim 3, it is characterised in that the polyalcohol or polyamine refer to containing multiple hydroxyls or ammonia
The compound of base, and F1For 3~6, specially trimethylolpropane, phloroglucin, 1,2,4,5- tetramino benzene hydrochlorides or double
Any one in pentaerythrite.
5. method according to claim 3, it is characterised in that the bromacyl bromide is 2- bromos propionyl bromide or the bromo- 2- of 2-
Methyl propionyl bromide.
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