CN105399880B - The method for preparing the equally distributed crosslinked polystyrene of branch point that can solve crosslinking - Google Patents
The method for preparing the equally distributed crosslinked polystyrene of branch point that can solve crosslinking Download PDFInfo
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- CN105399880B CN105399880B CN201510846285.5A CN201510846285A CN105399880B CN 105399880 B CN105399880 B CN 105399880B CN 201510846285 A CN201510846285 A CN 201510846285A CN 105399880 B CN105399880 B CN 105399880B
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- polystyrene
- branch point
- crosslinked polystyrene
- arm
- crosslinking
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 81
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 80
- 238000004132 cross linking Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 229920000768 polyamine Polymers 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 9
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000000463 material Substances 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- GHPHCDZRWUIBCE-UHFFFAOYSA-N 3-bromo-2-methylpropanoyl bromide Chemical class BrCC(C)C(Br)=O GHPHCDZRWUIBCE-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 125000001246 bromo group Chemical class Br* 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- RIBFXMJCUYXJDZ-UHFFFAOYSA-N propanoyl bromide Chemical compound CCC(Br)=O RIBFXMJCUYXJDZ-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 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
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001262 acyl bromides Chemical class 0.000 claims description 2
- 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 description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000021050 feed intake Nutrition 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical group CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 claims 1
- 238000007445 Chromatographic isolation Methods 0.000 claims 1
- 238000011097 chromatography purification Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 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 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000005859 coupling reaction Methods 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- -1 nitrogen-oxygen free radical Chemical class 0.000 description 8
- 229920006037 cross link polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 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
- 101710141544 Allatotropin-related peptide Proteins 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
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000005042 acyloxymethyl group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 229920002554 vinyl polymer Polymers 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
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 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
- ZPHQBFRCXUIIAZ-UHFFFAOYSA-N benzene;hydrochloride Chemical compound Cl.C1=CC=CC=C1 ZPHQBFRCXUIIAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to crosslinked polystyrene preparation, it is desirable to provide the method for preparing the equally distributed crosslinked polystyrene of branch point that can solve crosslinking.The method that the preparation can solve the equally distributed crosslinked polystyrene of branch point of crosslinking includes：Take the multi-arm polystyrene, copper powder, polyamine ligand of brominated end group to add in the reactor equipped with solvent, after deoxidation, stirring, the equally distributed crosslinked polystyrene of branch point that can solve crosslinking is made after reaction.The synthesis condition of the present invention is simple, and the synthesis of N bromine compounds is convenient, structurally variable, the N arm polystyrene brachiums degree of polymerization of brominated end group can accuracy controlling, be a kind of convenient, efficient crosslinked polystyrene new synthetic method.
Description
Technical field
The present invention is that the branch point of crosslinking can be solved by, which more particularly to preparing, is uniformly distributed on crosslinked polystyrene preparation field
Crosslinked polystyrene method.
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 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 to 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 mean molecule quantity 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
Characterize.(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
So that 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 to 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.)
Existing document report reacts free radical coupling for Macroscopic single crystal.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
Reducing agent research PS-Br ATRC reactions.(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 sign (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 chromatogram etc..Synthetic method main at present is to be copolymerized styrene and a small amount of divinylbenzene.Due to the polymerization of gained
Thing is insoluble not to be melted, and the structural information of polymer, such as crosslink density, crosslinking points distribution can not be directly obtained by existing characterization method
Deng.
The content of the invention
It is a primary object of the present invention to overcome deficiency of the prior art, there is provided it is a kind of solve crosslinking branch point it is uniform
The preparation method of the crosslinked polystyrene of distribution.In order to solve the above technical problems, the solution of the present invention is：
The method for preparing the equally distributed crosslinked polystyrene of branch point that can solve crosslinking is provided, is specially：
Take the multi-arm polystyrene of 1 part of brominated end group, the copper powder of 0.7N~10N parts, the polyamine ligand of 0.7N~10N parts
Add in the reactor equipped with solvent, after deoxidation, stirring, then reacted at 20~70 DEG C 21 minutes~48 hours, that is, being made can
Solve the equally distributed crosslinked polystyrene of branch point of crosslinking；
Wherein, the number to feed intake is molfraction；The arm number of the multi-arm polystyrene of brominated end group is N, and N is 3~6；
The polyamine ligand is using 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, N, N, N ', any one material in N '-four [(2- pyridine radicals) methyl] -1,2- ethylenediamines；
The solvent using tetrahydrofuran, 2- methyltetrahydrofurans, 1-METHYLPYRROLIDONE, N,N-dimethylformamide,
Any one material in dimethyl sulfoxide (DMSO), methyl phenyl ethers anisole.
In specific operation, it can use and add the multi-arm polystyrene of brominated end group, polyamine ligand, solvent instead
Answer in device, after carrying out deoxygenation three times using liquid nitrogen frozen-vacuum-melting circulation, add Cu powder under nitrogen protection, then carry out
Reaction, after reaction time (i.e. gel time) is reached, liquid nitrogen quenching terminating reaction is utilized after being further continued for reaction 1 hour, then
Extract 3 times at 60 DEG C with DMF, 40 DEG C be dried in vacuum overnight after obtain solving crosslinking the equally distributed crosslinking of branch point it is poly-
Styrene.
In the present invention, the branch point of obtained crosslinked polystyrene is evenly distributed, and the chain hop count that branch point is connected
It is between 3~6, i.e., identical with the arm number of the multi-arm polystyrene of brominated end group.
In the present invention, obtained crosslinked polystyrene can acid or alkali catalysis under, in the swollen state with monohydric alcohol
Or exchange reaction occurs at branch point for monoamine, degraded obtains dissolving in the line polymer (being defined as solution crosslinking) of solvent.
In the present invention, total polymerization shared by the network chain (chain that both ends are all connected with branch point) of obtained crosslinked polystyrene
The ratio (being defined as P) of thing chain can carry out accuracy controlling between 0.50~0.78.
In the present invention, (degree of polymerization of network chain is the network chain degree of polymerization of obtained crosslinked polystyrene between 5~100
Twice of the degree of polymerization of suspended chain, suspended chain refer to the chain that only one end is connected with branch point), and the network chain degree of polymerization be sized into
Row accuracy controlling.
In the present invention, the multi-arm polystyrene of the brominated end group can be prepared by following step：
(1) synthesis of polybromide：
1 part of polyalcohol or polyamine, F part triethylamines are dissolved in anhydrous methylene chloride, under ice cooling, 4 (slow) drop
Add 1.1F part bromacyl bromides, be stirred overnight (18 hours) at room temperature, it is then that reaction product is pure through recrystallization or column chromatography for separation
Change, that is, obtain polybromide, and the degree of functionality of polybromide is F, F is 3~6, the i.e. function with polyalcohol or polyamine
Spend identical；
The polyalcohol or polyamine are the compounds containing multiple hydroxyls or amino, and the function of polyalcohol or polyamine
Spend for F, and F is 3~6；Polyalcohol or polyamine are using trimethylolpropane, phloroglucin, two [(the bromo- 2- first of 2- of 2,2,2- tri-
The acyloxymethyl of base third) ethyl] ether, any one material in 1,2,4,5- tetramino benzene hydrochlorides；
The bromacyl bromide uses 2- bromos propionyl bromide or the bromo- 2- methyl propionyl bromides of 2-；
In specific operation, it can use and mix polyalcohol or polyamine, triethylamine, DCM, be placed in (three mouthfuls of container
Flask) in ice bath cool down；Then the DCM solution containing bromacyl bromide is instilled in container dropwise, dripped off within 1 hour, white occur
Precipitation, is warming up to room temperature (25 DEG C), is stirred overnight；Filtering, filtrate are washed three times with 50mL 1mol/L HCl solutions, saturation
NaHCO3The aqueous solution is washed three times, and 50mL deionized waters are washed three times, and 50mL saturations NaCl washed once, anhydrous MgSO4It is dried
Night；Filtering, after concentration, crude product is obtained, then, be dried in vacuo after filtering at 40 DEG C by crude product with methanol recrystallization twice
Night, that is, obtain polybromide；
(2) synthesis of the multi-arm polystyrene of brominated end group：
Take polybromide made from 1 part of step (1), and 10F~200F parts styrene monomer, 0.25F~5F part bromines
Change cuprous, 0.25F~5F parts N, N, N ', N ", N "-pentamethyldiethylenetriamine are added in reactor, after deoxidation, stirring, then
Reacted at 80~120 DEG C 0.5~8 hour, obtain the multi-arm polystyrene of brominated end group, and the multi-arm of brominated end group after purification
The arm number of polystyrene is N, and N is 3~6, i.e., identical with the degree of functionality of polybromide；
In specific operation, it can use after polybromide, PMDETA, styrene are added into reactor, first use
After liquid nitrogen frozen-vacuum-melting circulation carries out deoxygenation three times, CuBr is added under nitrogen protection, after reaching the reaction time, is utilized
Liquid nitrogen quenching terminating reaction；Then dissolve a polymer in DCM, post copper removal is crossed through neutral alumina, concentrate, then sunk with methanol
Form sediment, filtering, be dried in vacuum overnight at 40 DEG C, that is, obtain the multi-arm polystyrene of brominated end group；
In the present invention, the degree of polymerization of the multi-arm polystyrene of obtained brominated end group is 5F~100F, and F closes for more brominations
The degree of functionality of thing.
The operation principle of the present invention：Contain bromine end group by the way that ATRP (ATRP) synthesis is a series of first
And the uniform multi-arm polystyrene of brachium, there is reactive group at the branch point of multi-arm polystyrene, such as ester group or acid amides
Base；Under copper/part effect, the multi-arm polystyrene (3≤arm number N≤6) of different brominated end groups produces carbon radicals, occurs
Free radical coupling reacts, can obtain crosslinked polystyrene (course of reaction as shown in schematic diagram 1, using initiator containing tribromo as
Example).
Two kinds of chains are included in the network structure of cross-linked polymer.A kind of is the chain that both ends are all connected with branch point, is referred to as
Network chain；Another kind is the chain that only one end is connected with branch point, referred to as suspended chain.Because the brachium of multiarm polymers is uniform
, a coupling reaction, which often occurs, will produce a network chain, so the length of network chain is also uniform.It is that is, branched
The distance between point is uniform.A coupling reaction, which often occurs, will produce a network chain, reduce by 2 suspended chains, so net
Ratio shared by chain is related to coupling degree.By controlling reaction condition, it (or is anti-that can obtain end group coupling degree
Answer degree) different product.So the mass ratio of total polymer chain (is defined as shared by control coupling degree can regulation and control network chain
P).In addition according to our method, the molecular weight of network chain is twice of the molecular weight of suspended chain.
Due to having ester group or amide groups at branch point, under the catalysis of acid or alkali, state of the cross-linked polymer in swelling
Under exchange reaction can occur with monohydric alcohol or amine, obtain dissolving in the line polymer of solvent.We are being crosslinked this kind of
The cross-linked polymer that degradation reaction occurs at point is defined as solving the polymer of crosslinking.The product after being crosslinked will be solved and carry out gel color
Stave is levied, and with peak-fit processing and can be calculated the mass ratio (P) of total polymer chain shared by network chain.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, synthesis condition of the invention is simple, and the synthesis of N bromine compounds is convenient, structurally variable, the N arm polyphenyl second of brominated end group
The alkene brachium degree of polymerization can accuracy controlling, be a kind of convenient, efficient crosslinked polystyrene new synthetic method.
2nd, the conversion ratio of crosslinked polystyrene produced by the present invention can be close to 100%, and reactivity is high, preparation condition temperature
With；The crosslinked polystyrene has degradable branch point, can be degraded into crosslinked polystyrene at branch point by reacting
For linear polystyrene.
Brief description of the drawings
Fig. 1 is the schematic diagram that tribromo initiator prepares crosslinked polystyrene.
Fig. 2 is the GPC spectrograms and its swarming fitting result after the crosslinking of crosslinked polystyrene solution in embodiment 21.
Embodiment
The present invention is described in further detail with embodiment below in conjunction with the accompanying drawings：
The present invention is more fully understood in the professional and technical personnel that the following examples can make this professional, but not with any side
The formula limitation present invention.In the following embodiments, all polymerisations are carried out under the anhydrous reaction condition of anaerobic.
It is as follows for the polybromide molecular formula in embodiment：
It is as follows for the abbreviation in embodiment：
THF：Tetrahydrofuran；Me-THF：2- methyltetrahydrofurans；NMP：1-METHYLPYRROLIDONE；DMF：N, N- dimethyl
Formamide；DMSO：Dimethyl sulfoxide (DMSO)；Anisole：Methyl phenyl ethers anisole；DCM：Dichloromethane；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) first
Base] amine；TPEN：N, N, N ', N '-four [(2- pyridine radicals) methyl] -1,2- ethylenediamines.
The polyamine ligand TPMA of embodiment 1 synthesis
16.4g 2- chloromethyl pyridine hydrochlorides (0.1mol) are dissolved in 40mL deionized waters, ice bath cooling, slowly added
Enter dissolved with the 0.1mol sodium hydroxide 20mL aqueous solution, 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 the 0.1mol sodium hydroxide 20mL aqueous solution, 50 is small
When drip off.Stopping reaction, organic phase is washed with 3 × 10mL 15%NaOH aqueous solution, 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).Elementary analysis：Survey
Value (theoretical value):C,74.38(74.46)；H,6.29(6.25).
The polyamine ligand TPEN of embodiment 2 synthesis
13.12g 2- chloromethyl pyridine hydrochlorides (0.08mol) are dissolved in 30mL deionized waters, ice bath cooling, slowly
Add dissolved with the 0.08mol sodium hydroxide 15mL aqueous solution, 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 the 0.08mol sodium hydroxide 15mL aqueous solution, 50
Hour drips off.Stop reaction, wash organic phase with 3 × 10mL 15%NaOH aqueous solution, 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).Elementary analysis：Measured value (theoretical value):C,73.48(73.56)；H,6.67(6.65).
The initiator 3a of embodiment 3 synthesis
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, drip off within 1 hour, white precipitate occur, be warming up to room temperature (25 DEG C), stir
Mix overnight.Filtering, filtrate are washed three times with 50mL 1mol/L HCl solutions, saturation NaHCO3The aqueous solution is washed three times, and 50mL is gone
Three times, 50mL saturations NaCl washed once ion water washing, anhydrous MgSO4It is dried overnight.Filtering, after concentration, obtains yellow and glues
Thick 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-).Elementary analysis：Measured value (theoretical value):C,37.09
(37.20)；H,5.05(5.03).
The initiator 3b of embodiment 4 synthesis
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-).Elementary analysis：Measured value (theoretical value):C,33.29(33.42)；H,4.31
(4.30)。
The initiator 3c of embodiment 5 synthesis
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).Elementary analysis：Measurement
It is worth (theoretical value):C,37.52(37.73)；H,3.72(3.69).
The initiator 4a of embodiment 6 synthesis
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, drips off within 1 hour, white precipitate occurs, be 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-).Elementary analysis：Measured value (theoretical value):C,35.32
(35.99)；H,4.14(4.12)；N,7.61(7.63).
The initiator 6a of embodiment 7 synthesis
By 5.41g bis- [2,2,2- tri- (the bromo- 2- methyl-props acyloxymethyls of 2-) ethyl] ether (2 × 10-2Mol), the second of 17mL tri-
Amine (12 × 10-2Mol), 50mL DCM are mixed, and are placed in 250mL three-necked flasks, ice bath cooling.16.5mL2- bromos third will be contained
Acylbromide (13.2 × 10-2Mol DCM solution (50mL)) is instilled in three-necked flask dropwise, drips off within 1 hour, white precipitate occurs, is risen
(25 DEG C) are warmed to room temperature, are stirred 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-).Elementary analysis：Measured value (theoretical value):C,34.40(35.57)；H,4.61(4.57).
The synthesis of 3 arm polystyrene (TPSa1) of 8 brominated end group of embodiment
By 1.06g initiators 3a (2 × 10-3Mol), 360 μ L PMDETA (1.5 × 10-3Mol) and 7mL styrene (6 ×
10-2Mol) add in 10mL pyriform Schlenk bottles.After liquid nitrogen frozen-vacuum-melting circulates deoxygenation three times, under nitrogen protection
Add 212mg CuBr (1.5 × 10-3mol).At 80 DEG C, react 4 hours, liquid nitrogen quenching terminating reaction.Polymer is dissolved in DCM
In, post copper removal is crossed through neutral alumina, is concentrated.With methanol extraction, filtering, 40 DEG C are dried in vacuum overnight, and obtain white powder
Solid.Resulting polymers are tested through gel permeation chromatography (GPC)：Number-average molecular weight (Mn)=1490g/mol, molecular weight distribution refer to
Number (PDI)=1.13.Through1H NMR(400MHz,CDCl3) the measuring and calculation degree of polymerization is about 15, i.e., single armed is 5 styrene lists
Member.
The synthesis of 3 arm polystyrene (TPSa2-TPSa8) of the brominated end groups of embodiment 9-15
According to the operation of embodiment 8, rate of charge, temperature and the control polymerization time of feed change, TPSa2- is respectively synthesized
TPSa8, specific reaction condition and result are as shown in table 1.
Initiator 3a degree of functionality F is 3, and the number that styrene monomer is added in embodiment 8,9 is 10 × 3；Embodiment 10-
The number that monomer is added in 12 is that the number of addition monomer in 50 × 3, embodiment 13-15 is 200 × 3；
Added in embodiment 8,9 mantoquita number be added in 0.25 × 3, embodiment 10,11 mantoquita number be 0.5 × 3, reality
It is that addition mantoquita number is to add mantoquita in 2 × 3, embodiment 14,15 in 1 × 3, embodiment 13 to apply and mantoquita number is added in example 12
Number is 5 × 3；
It is equal with mantoquita to add number for part in each embodiment；
Specific polymerizing condition and result are as shown in table 1.
The polymerizing condition and result of 3 arm polystyrene of brominated terminal in the embodiment 8-15 of table 1
*Reaction condition：Initiator：3a；Part：PMDETA.
The synthesis of the multi-arm polystyrene (TPSb1, TPSc1, QPSa1, HPSa1) of other brominated end groups of embodiment 16-19
According to the operation of embodiment 8, initiator 3b, 3c, 4a, 6a is respectively adopted in embodiment 16-19, be respectively synthesized TPSb1,
TPSc1、QPSa1、HPSa1；
Specific polymerizing condition and result are as shown in table 2.
The polymerizing condition and result of other multi-arm polystyrene in the embodiment 16-19 of table 2
*Reaction condition：Temperature：100℃；Part：PMDETA；Polymerization time：8 hours.
The preparation of the crosslinked polystyrene of embodiment 20
The arm polystyrene TPSa2 (2 × 10 of 62mg tri--5Mol), 18mg TPMA (6 × 10-5Mol) and 2mL THF are added
In 10mL straight Schlenk bottles.Liquid nitrogen frozen-vacuum-melting circulation after deoxygenation, adds 4mg Cu powder under nitrogen protection three times
(6×10-5mol).At 60 DEG C, reaction obtains g., jelly-like solid in 48 hours, continues liquid nitrogen quenching terminating reaction after reacting 1 hour.
Extract 3 times at 60 DEG C with 10mL DMF, 40 DEG C be dried in vacuum overnight after obtain faint yellow flexible solid globules.
The preparation of crosslinked polystyrene under the conditions of embodiment 21-43 differential responses
According to the operation of embodiment 20, it is prepared for using different monomers concentration, different solvents, different temperatures, different ligands
A series of crosslinked polystyrenes, specific reaction condition and result are as shown in table 3.
BPY, DNBPY, PMDETA, HMTETA, Me has been respectively adopted in wherein embodiment 20-266- TREN, TPMA or
Polyamine ligands different TPEN；
Different molten of THF, Me-THF, NMP, DMF, DMSO or Anisole has been respectively adopted in embodiment 25 and 27-31
Agent；
Embodiment 25 and 32-36 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 41-43；
It is equal with copper powder to add number for part in each embodiment；
Specific preparation condition and result are as shown in table 3
The preparation condition and result of crosslinked polystyrene are prepared in the embodiment 20-43 of table 3 under the conditions of differential responses
*Reaction condition：Monomer：TPSa2；Solvent：THF.
The preparation of the different crosslinked polystyrene of chain length between embodiment 44-51 branch points
According to the operation of embodiment 20, with the different crosslinking polyphenyl second of chain length between the synthesizing branched points of TPSa1-TPSa8
Alkene；
Specific reaction condition and result are as shown in table 4.
In the embodiment 44-51 of table 4 between branch point the different crosslinked polystyrene of chain length preparation condition and result
*Reaction condition：Monomer concentration：0.02mol/L；Part：TPMA；Temperature：60℃；Solvent：THF.
The preparation of the crosslinked polystyrene of embodiment 52-59 difference network chain ratios (P)
According to the operation of embodiment 20, continue the time of reaction after control gel-forming, the crosslinking for preparing different P values gathers
Styrene；
Specific reaction condition and result are as shown in table 5.
The preparation condition and result of the crosslinked polystyrene of different network chain ratios (P) in the embodiment 52-59 of table 5
*Reaction condition：[TPSa2]=0.02mol/L；Part：TPMA；Rate of charge：[monomer]:[copper]:[part]=1:
3:3；Temperature：60℃；Solvent：THF.
**P calculation is referring to embodiment 64
The preparation of the crosslinked polystyrene of embodiment 60-63 difference branching units
According to the operation of embodiment 20, prepared and handed over using TPSb1, TPSc1, QPSa1, HPSa1 multi-arm polystyrene monomers
Polystyrene.Specific reaction condition and result are as shown in table 6.
The preparation condition and result of the crosslinked polystyrene of different branching units in the embodiment 60-63 of table 6
*Reaction condition：Monomer concentration：0.02mol/L；Part：TPMA；Temperature：60℃；Solvent：THF.
**P calculation is referring to embodiment 64
The solution crosslinking and the calculating of network chain ratio (P) of the crosslinked polystyrene of embodiment 64
Crosslinked polystyrene sample (50mg-200mg) and 30mL THF are added in 100mL flasks, stirred at 60 DEG C
Swelling.After 30 minutes, in four batches, every 30 minutes, it is added dropwise dissolved with 0.02mol highly basic (potassium hydroxide or sodium hydroxide) or strong
The methanol or n-butylamine solution 20mL of sour (sulfuric acid or p-methyl benzenesulfonic acid).Solvent is spin-dried for after continuing reaction 24 hours, with
CH2Cl2/H2O systems extract, and collect oil phase, then be washed with deionized water to neutrality.Solvent is spin-dried for, obtains the linear polyphenyl of solution crosslinking
Ethene sample.
The GPC spectrograms for solving cross-linked samples are subjected to swarming fitting (as shown in Figure 1) with Gauss methods, one times point can be obtained
The peak Peak 1 (corresponding to suspended chain) and twice of molecular weight of son amount peak Peak 2 (corresponding to network chain).Can be with by integration method
Respectively obtain Peak 1 area S1 and Peak 2 area S2.
Then the ratio P of total polymer chain shared by network chain calculation formula is as follows：P=S2/ (S1+S2).
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, there can also be many variations.One 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 (7)
1. prepare the method for the equally distributed crosslinked polystyrene of branch point that can solve crosslinking, it is characterised in that be specially：
The polyamine ligand of the multi-arm polystyrene of 1 part of brominated end group, the copper powder of 0.7N~10N parts, 0.7N~10N parts is taken to add
In reactor equipped with solvent, after deoxidation, stirring, then reacted at 20~70 DEG C 21 minutes~48 hours, that is, friendship can be solved by being made
The equally distributed crosslinked polystyrene of branch point of connection；
Wherein, the number to feed intake is molfraction；The arm number of the multi-arm polystyrene of brominated end group is N, and N is 3~6；
The polyamine ligand is using 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, N, N, N ', any one material in N '-four [(2- pyridine radicals) methyl] -1,2- ethylenediamines；
The solvent is using tetrahydrofuran, 2- methyltetrahydrofurans, 1-METHYLPYRROLIDONE, N,N-dimethylformamide, diformazan
Any one material in base sulfoxide, methyl phenyl ethers anisole.
2. preparation according to claim 1 can solve the method for the equally distributed crosslinked polystyrene of branch point of crosslinking, its
It is characterised by, the branch point of obtained crosslinked polystyrene is evenly distributed, and the chain hop count that branch point is connected is between 3~6,
It is i.e. identical with the arm number of the multi-arm polystyrene of brominated end group.
3. preparation according to claim 1 can solve the method for the equally distributed crosslinked polystyrene of branch point of crosslinking, its
It is characterised by, obtained crosslinked polystyrene can exist with monohydric alcohol or monoamine in the swollen state under the catalysis of acid or alkali
Exchange reaction occurs at branch point, degraded obtains dissolving in the line polymer of solvent.
4. preparation according to claim 1 can solve the method for the equally distributed crosslinked polystyrene of branch point of crosslinking, its
It is characterised by, the ratio of total polymer chain shared by the network chain of obtained crosslinked polystyrene, and can between 0.50~0.78
Carry out accuracy controlling.
5. preparation according to claim 1 can solve the method for the equally distributed crosslinked polystyrene of branch point of crosslinking, its
It is characterised by, the network chain degree of polymerization of obtained crosslinked polystyrene is between 5~100, and the network chain degree of polymerization is sized to carry out
Accuracy controlling.
6. preparation according to claim 1 can solve the method for the equally distributed crosslinked polystyrene of branch point of crosslinking, its
It is characterised by, the multi-arm polystyrene of the brominated end group can be prepared by following step：
(1) synthesis of polybromide：
1 part of polyalcohol or polyamine, F part triethylamines are dissolved in anhydrous methylene chloride, 1.1F part bromines are added dropwise under ice cooling, 4
For acylbromide, it is stirred overnight at room temperature, then reaction product is obtained more brominations and closed through recrystallization or column chromatographic isolation and purification
Thing, and the degree of functionality of polybromide is F, F is 3~6, i.e., identical with the degree of functionality of polyalcohol or polyamine；
The polyalcohol or polyamine are the compounds containing multiple hydroxyls or amino, and the degree of functionality of polyalcohol or polyamine is
F, and F is 3~6；Polyalcohol or polyamine are using trimethylolpropane, phloroglucin, two [(the bromo- 2- methyl-props of 2- of 2,2,2- tri-
Acyloxymethyl) ethyl] ether, any one material in 1,2,4,5- tetramino benzene hydrochlorides；
The bromacyl bromide uses 2- bromos propionyl bromide or the bromo- 2- methyl propionyl bromides of 2-；
(2) synthesis of the multi-arm polystyrene of brominated end group：
Take polybromide made from 1 part of step (1), and 10F~200F parts styrene monomer, 0.25F~5F part protobromides
Copper, 0.25F~5F parts N, N, N ', N ", N "-pentamethyldiethylenetriamine are added in reactor, after deoxidation, stirring, then 80~
Reacted at 120 DEG C 0.5~8 hour, obtain the multi-arm polystyrene of brominated end group, and the multi-arm polyphenyl of brominated end group after purification
The arm number of ethene is N, and N is 3~6, i.e., identical with the degree of functionality of polybromide；
Wherein, the number for reacting addition is molfraction.
7. preparation according to claim 6 can solve the method for the equally distributed crosslinked polystyrene of branch point of crosslinking, its
It is characterised by, the degree of polymerization of the multi-arm polystyrene of obtained brominated end group is 5F~100F, and F is the function of polybromide
Degree.
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