CN104277184B - A kind of preparation method of 2-chlorine trityl group chlorine resin - Google Patents
A kind of preparation method of 2-chlorine trityl group chlorine resin Download PDFInfo
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- CN104277184B CN104277184B CN201410482405.3A CN201410482405A CN104277184B CN 104277184 B CN104277184 B CN 104277184B CN 201410482405 A CN201410482405 A CN 201410482405A CN 104277184 B CN104277184 B CN 104277184B
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- microsphere
- chlorine
- trityl group
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- polystyrene
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- 239000000460 chlorine Substances 0.000 title claims abstract description 165
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 165
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims abstract description 77
- 229920005989 resin Polymers 0.000 title claims abstract description 72
- 239000011347 resin Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000004005 microsphere Substances 0.000 claims abstract description 163
- 239000004793 Polystyrene Substances 0.000 claims abstract description 107
- 229920002223 polystyrene Polymers 0.000 claims abstract description 106
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 69
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 47
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims abstract description 46
- 239000004141 Sodium laurylsulphate Substances 0.000 claims abstract description 45
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 39
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 39
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 32
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 32
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 230000008961 swelling Effects 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000000839 emulsion Substances 0.000 claims description 39
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 239000012071 phase Substances 0.000 claims description 31
- 239000008346 aqueous phase Substances 0.000 claims description 28
- 238000013019 agitation Methods 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 25
- -1 (2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl Chemical group 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- GRDGBWVSVMLKBV-UHFFFAOYSA-N (2-amino-5-nitrophenyl)-(2-chlorophenyl)methanone Chemical compound NC1=CC=C([N+]([O-])=O)C=C1C(=O)C1=CC=CC=C1Cl GRDGBWVSVMLKBV-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- MCZQGJXPPZHLTG-UHFFFAOYSA-N C.[Cl] Chemical compound C.[Cl] MCZQGJXPPZHLTG-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000013517 stratification Methods 0.000 claims description 2
- HLTUZPFCDXKNKS-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene ethene Chemical group C(=C)C1=C(C=CC=C1)C=C.C=C HLTUZPFCDXKNKS-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims 1
- 238000003810 ethyl acetate extraction Methods 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 13
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000007385 chemical modification Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000011806 microball Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 108090000765 processed proteins & peptides Proteins 0.000 description 7
- JFLSOKIMYBSASW-UHFFFAOYSA-N 1-chloro-2-[chloro(diphenyl)methyl]benzene Chemical compound ClC1=CC=CC=C1C(Cl)(C=1C=CC=CC=1)C1=CC=CC=C1 JFLSOKIMYBSASW-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002525 ultrasonication Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 102000004196 processed proteins & peptides Human genes 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- 239000013504 Triton X-100 Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HDPRNQWMIFKNKS-UHFFFAOYSA-N benzene;lithium Chemical compound [Li].C1=CC=CC=C1 HDPRNQWMIFKNKS-UHFFFAOYSA-N 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002024 ethyl acetate extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 2
- 239000013598 vector Substances 0.000 description 2
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- HBAHZZVIEFRTEY-UHFFFAOYSA-N 2-heptylcyclohex-2-en-1-one Chemical compound CCCCCCCC1=CCCCC1=O HBAHZZVIEFRTEY-UHFFFAOYSA-N 0.000 description 1
- HIBWGGKDGCBPTA-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 HIBWGGKDGCBPTA-UHFFFAOYSA-N 0.000 description 1
- ZXNCFNXSRFWJKP-UHFFFAOYSA-N CClC1=CC=CC=C1 Chemical compound CClC1=CC=CC=C1 ZXNCFNXSRFWJKP-UHFFFAOYSA-N 0.000 description 1
- 108010032976 Enfuvirtide Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 229920001367 Merrifield resin Polymers 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 108010037251 peptide T1249 Proteins 0.000 description 1
- 238000010647 peptide synthesis reaction Methods 0.000 description 1
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 108010004034 stable plasma protein solution Proteins 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention discloses the preparation method of a kind of 2 chlorine trityl group chlorine resins, it is characterized in that, comprise the following steps: use 2 chlorine trityl group chlorine monomers, styrene and the divinylbenzene of polystyrene microsphere seed swelling band double bond, with benzoyl peroxide as initiator, polyvinyl alcohol is stabilizer, sodium lauryl sulphate is emulsifying agent, prepares 2 chlorine trityl group chlorine resin microspheres.The present invention uses " seed law " step to prepare homogeneous, monodispersed 2 chlorine trityl group chlorine resin microspheres, method is simple, it is not necessary to remakes chemical modification after obtaining microsphere, reduces environmental pollution, can extensively apply as solid phase synthesis resin, there is the highest market using value.
Description
Technical field
The present invention relates to 2-chlorine trityl group chlorine resin, in particular, a kind of 2-chlorine triphenyl
The preparation method of methyl chloride resin.
Background technology
The full chemosynthesis of polypeptide is divided into liquid phase and solid phase synthesis, Solid phase peptide synthssis (Solid Phase
Peptide Synthesis, SPPS) method since within 1963, founding, because it is easy and simple to handle, by-product is few,
Purification efficiency advantages of higher, is increasingly used for the research and development of biological activity peptides, particularly
It is widely used in the actual production of medicinal small peptide.
In Solid-phase synthesis peptides, 2-chlorine trityl chloride (2-Chlorotritylchloride, 2-CTC)
Resin has reaction condition relatively other resin milders, can effectively suppress racemization and diketopiperazine
The generations of side reaction such as generation, product purity advantages of higher, be applied to multiple polypeptides medicine such as cell
Merging the industrialized production of enzyme inhibition peptide T20 and T1249 etc. 2-CTC resin can be additionally used in carboxylic in addition
Acid, alcohol and the solid phase synthesis of mercaptan, purposes and excellent performance determine it no longer simply in fact widely
Test the synthetic vectors that room is conventional, and the production vector resin that high-volume uses will be increasingly becoming.
Preparation 2-chlorine trityl group chlorine solid phase synthesis resin mainly has three kinds of methods, mainly at polyphenyl
Introducing 2-CTC structure on ethylene carrier, one is to obtain by iodobenzene polymer and n-BuLi are derivative
Lithium-benzene polymer, then reacted generation trityl polymer by lithium-benzene polymer and benzophenone；Two are
First obtained benzophenone by polystyrene resin and Benzenecarbonyl chloride. by Friedel-Crafts acylation reaction to derive
Polymer, then by organolithium reagent, benzophenone derived polymer is converted into trityl polymer；
Alternatively, it is also possible to be directly connected on Merrifield resin by trityl, but the method needs first molten
Trityl alcohol is prepared as connecting precursor with organometallic reagent under liquid status；In addition, pass through
Tritylated monomer polymerization preparation 2-CTC resin needs to use Grignard reagent or organolithium reagent.On
State method step more complicated and be both needed to use organometallic reagent, operation condition, reagent cost and
The process of waste material all may become more scabrous problem in 2-CTC resin large-scale production.
Additionally, " the process engineering journal " in June, 2009 discloses " 2-chlorine trityl chloride resin
Preparation and application in Solid-phase synthesis peptides ", describe with 2-chlorobenzophenone as raw material, with
PCl5 adds thermal synthesis 1-chloro-2-dichlorobenzyl benzene as precursor at 130～140 DEG C, is less than with particle diameter
1.5% divinylbenzene crosslink polystyrene resin of 30 μm carries out Friedel-Crafts alkylated reaction,
Gained 2-chlorine trityl alcohol thionyl chloride carries out chloridized, obtains 2-chlorine trityl chloride resin.
But, these methods of prior art are modified after being all based on the chemistry of microsphere, and step is loaded down with trivial details,
Environmental pollution is serious.
Summary of the invention
The technical problem to be solved is to provide a kind of new 2-chlorine trityl group chlorine resin
Preparation method.
Technical scheme is as follows: the preparation method of a kind of 2-chlorine trityl group chlorine resin, its
Comprise the following steps: use the 2-chlorine trityl group chlorine list of polystyrene microsphere seed swelling band double bond
Body, styrene and divinylbenzene, with benzoyl peroxide as initiator, polyvinyl alcohol is stabilizer,
Sodium lauryl sulphate is emulsifying agent, prepares 2-chlorine trityl group chlorine resin microsphere.
Preferably, after preparing 2-chlorine trityl group chlorine resin microsphere, described microsphere is carried out
Clean, then dry
Preferably, the 2-chlorine trityl group chlorine monomer of described band double bond be ((2 '-chloro-phenyl)-(4 '-
Ethenylphenyl)-phenyl) chloromethanes.
Preferably, by ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) methanol and thionyl chloride
Reaction, obtains ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) chloromethanes.
Preferably, chloro-for 1-2-(dichloro (benzene) methyl) benzene, styrene are reacted with aluminum chloride,
It is subsequently adding water stopped reaction, then is extracted with ethyl acetate, afterwards by ethyl acetate layer saturated common salt
Water washs, and anhydrous sodium sulfate is dried, and 50 DEG C of decompression rotary evaporations, to residual liquid, stop rotation and steam,
Stand, separate out ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) methanol.
Preferably, neighbour's chlorobenzophenone and phosphorus pentachloride are joined in reaction bulb, mechanical agitation, rise
Temperature is reacted to 135 DEG C, and reaction adds frozen water, separatory after stirring after terminating；Lower floor's liquid frozen water
Clean, obtain the chloro-2-of 1-(dichloro (benzene) methyl) benzene.
Preferably, described polystyrene microsphere seed is 25 μm polystyrene microspheres of uniform particle diameter.
Preferably, described preparation method comprises the following steps: preparation polystyrene polymeric microsphere reaction
The aqueous phase solution of system, wherein contains polyvinyl alcohol 10g/L, containing sodium lauryl sulphate 2.5g/L；Take portion
Divide described aqueous phase solution, by the polystyrene microsphere suspended dispersed of monodispersed 25 μm uniform particle diameter in water
In phase solution, the wherein 2.5g/L Han polystyrene microsphere, obtain polystyrene seed microsphere suspended dispersed molten
Liquid；Benzoyl peroxide is dissolved in containing ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) chlorine
Methane, in styrene monomer, and the mixed liquor of divinylbenzene, obtains oily solution, wherein,
The mass percent of benzoyl peroxide is 0.9% to 1.1%；Separately take the described aqueous phase solution of part, by institute
State oily solution and join in aqueous phase solution, obtain the mixed system of water-oil phase layering, ultrasonic mixing
Making emulsion, wherein, scattered oiliness droplet diameter is less than 1 μm；Polystyrene seed is micro-
Ball suspended dispersed solution joins described emulsion, is placed in 20 DEG C to 45 DEG C oil baths, makees in mechanical agitation
Under with after swelling 15 to 30 hours, it is warmed up to 66 DEG C to 82 DEG C and keeps mechanical agitation to carry out polymerization instead
Answer 20 to 32 hours, with lauryl sodium sulfate aqueous solution gravitational settling classification, remove small particle
Polystyrene microsphere, obtains the 2-chlorine trityl group chlorine resin microsphere of uniform particle diameter.
Preferably, benzoyl peroxide is 0.98% to 0.99%:1 with the mass percent of described mixed liquor；
In the mixed system of water-oil phase layering, the volume ratio of water-oil phase is 1:(1.8 to 4.2)；Described oil
The temperature of bath is 30 DEG C；Described mechanical agitation rotating speed is 150rpm, time swelling under mechanical agitation
Between be 18 hours, be warmed up to 75 DEG C and keep mechanical agitation to carry out polyreaction 24 hours, obtaining
The lauryl sodium sulfate aqueous solution 500mL gravitational settling classification of product 2.5g/L 3 times, removes micro-
A small amount of polystyrene microsphere of small particle, obtains the 2-chlorine trityl group chlorine resin microsphere of uniform particle diameter.
Preferably, described preparation method further comprises the steps of: the described 2-chlorine trityl group chlorine resin of employing
2-chlorine trityl group chlorine resin prepared by microsphere.
Using such scheme, the present invention uses " seed law " step to prepare homogeneous, single dispersing
2-chlorine trityl group chlorine resin microsphere, method is simple, it is not necessary to remakes chemistry after obtaining microsphere and repaiies
Decorations, reduce environmental pollution, extensively can apply as solid phase synthesis resin, and having the highest market should
By value.
Accompanying drawing explanation
Fig. 1 is the reaction schematic diagram of one embodiment of the present of invention；
Fig. 2 is the monomer preparation reaction schematic diagram of one embodiment of the present of invention；
Fig. 3 is the 2-chlorine trityl group chlorine resin-made standby reaction schematic diagram of one embodiment of the present of invention；
Fig. 4 is the electron micrograph of one embodiment of the present of invention.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with the accompanying drawings and specific embodiment, the present invention is carried out more
Detailed description.It should be noted that when element is expressed " being fixed on " another element, and it can
With directly on another element or one or more element placed in the middle can be there is therebetween.When one
Individual element is expressed " connection " another element, it can be directly to another element or
One or more element placed in the middle can be there is therebetween in person.Term " vertical " that this specification is used,
" level ", "left", "right" and similar statement are for illustrative purposes only.
Unless otherwise defined, this specification is used all of technology and scientific terminology with belong to this
The implication that bright those skilled in the art are generally understood that is identical.Saying in the present invention in this specification
Term used in bright book is intended merely to describe the purpose of specific embodiment, is not intended to limit this
Invention.The term "and/or" that this specification is used includes one or more relevant Listed Items
Arbitrary and all of combination.
As it is shown in figure 1, one embodiment of the present of invention is, a kind of 2-chlorine trityl group chlorine resin
Preparation method, it comprises the following steps: use the 2-chlorine three of polystyrene microsphere seed swelling band double bond
Phenyl methyl chlorine monomer, styrene and divinylbenzene, with benzoyl peroxide as initiator, poly-second
Enol is stabilizer, and sodium lauryl sulphate is emulsifying agent, prepares 2-chlorine trityl group chlorine tree
Lipoid microsphere.Such as, preparation method is divided into three below step: 1, prepare polystyrene microsphere seed；
2, the 2-chlorine trityl group chlorine monomer of band double bond is prepared；3, with the 2-chlorine trityl group chlorine of double bond
Monomer, styrene, divinylbenzene press different proportion allotment, obtain the different degree of cross linking, different carrying capacity
2-chlorine trityl group chlorine solid phase synthesis resin microsphere, there is the highest practical value.Wherein,
The degree of cross linking and carrying capacity can determine according to logical reasoning or limited experimentation.
Such as, the preparation method of a kind of 2-chlorine trityl group chlorine resin, it comprises the following steps: adopt
With 2-chlorine trityl group chlorine monomer, styrene and the diethyl of polystyrene microsphere seed swelling band double bond
Alkenyl benzene, with benzoyl peroxide as initiator, polyvinyl alcohol is stabilizer, sodium lauryl sulphate
For emulsifying agent, prepare 2-chlorine trityl group chlorine resin microsphere；Preferably, described preparation method
Further comprise the steps of: the described 2-chlorine trityl group chlorine resin microsphere of employing and prepare 2-chlorine trityl group chlorine
Resin.And for example, these 2-chlorine triphens are used after preparing 2-chlorine trityl group chlorine resin microsphere
Ylmethyl chlorine resin microsphere prepares 2-chlorine trityl group chlorine resin.Such as, divinylbenzene is to two
Vinyl benzene.Preferably, described polystyrene microsphere seed is that 25 μm polystyrene of uniform particle diameter are micro-
Ball；Such as, the PS microsphere of 4.5 μm uniform particle diameter, swelling styrene (Styrene, C are used8H8),
Again it is polymerized, obtains the PS microsphere of 25 μm uniform particle diameter.Preferably, 2-chlorine triphenyl is prepared
After methyl chloride resin microsphere, described microsphere is carried out, then dries；Preferably, it is prepared into
After 2-chlorine trityl group chlorine resin microsphere, described microsphere organic reagent is cleaned, then dries
Dry；Described organic reagent includes acetone, dichloromethane and/or methanol etc..Such as, 2-chlorine is prepared
After trityl group chlorine resin microsphere, described microsphere acetone, dichloromethane and/or methanol are cleaned,
Then dry；Then 2-chlorine trityl group chlorine resin prepared by the microsphere after using these to dry.Wherein,
The 2-chlorine trityl group chlorine monomer of described band double bond be ((2 '-chloro-phenyl)-(4 '-thiazolinyl phenyl)-
Phenyl) chloromethanes；Such as, the 2-chlorine trityl group chlorine monomer of described band double bond is ((2 '-chloro-benzene
Base)-(4 '-ethenylphenyl)-phenyl) chloromethanes.The examples below is mainly with ((2 '-chloro-phenyl)
-(4 '-ethenylphenyl)-phenyl) as a example by chloromethanes, the 2-chlorine trityl group chlorine monomer of band double bond
Can also be selected other in addition to ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) chloromethanes
Stability Analysis of Structures, the most low-cost 2-chlorine trityl group chlorine monomer with double bond.Preferably,
((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) chloromethanes, styrene and divinylbenzene
Mass ratio is (1 to 5): (1 to 5): (0.05 to 0.1), and such as, the mass ratio of three is (1
To 4): (1 to 4): (0.05 to 0.1)；And for example, the mass ratio of three is (2 to 3): (2
To 3): (0.05 to 0.075)；Preferably, ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl)
Chloromethanes and cinnamic gross mass, be 8:0.1, such as, ((2 '-chlorine with the mass ratio of divinylbenzene
-phenyl)-(4 '-ethenylphenyl)-phenyl) chloromethanes and cinnamic mass ratio be (2 to 3): (2
To 3)；Preferably, both mass ratioes are 1:1.
Such as, the preparation method of a kind of 2-chlorine trityl group chlorine resin, it comprises the following steps: adopt
With 2-chlorine trityl group chlorine monomer, styrene and the diethyl of polystyrene microsphere seed swelling band double bond
Alkenyl benzene, with benzoyl peroxide as initiator, polyvinyl alcohol is stabilizer, sodium lauryl sulphate
For emulsifying agent, prepare 2-chlorine trityl group chlorine resin microsphere；Wherein, polystyrene microsphere kind
Son is placed in the aqueous phase solution of polystyrene polymeric microsphere reaction system；Such as, described aqueous phase solution
In containing polyvinyl alcohol 8-20g/L, containing sodium lauryl sulphate 1.5-4g/L；And for example, described aqueous phase solution
In containing polyvinyl alcohol 8-15g/L, containing sodium lauryl sulphate 2-3g/L；Preferably, described aqueous phase solution
Containing polyvinyl alcohol 10g/L, containing sodium lauryl sulphate 2.5g/L.Then, by monodispersed, particle diameter is equal
The polystyrene microsphere suspended dispersed of one, in aqueous phase solution, obtains the suspension point of polystyrene seed microsphere
Dissipate solution.Such as, polystyrene microsphere particle diameter is that 20 μm are to 30 μm, and for example, polystyrene microsphere
Particle diameter is that 22 μm are to 28 μm；Preferably, polystyrene microsphere particle diameter is 25 μm.Such as, wherein,
Polystyrene seed microsphere suspended dispersed solution 1.5-5g/L Han polystyrene microsphere, and for example, polystyrene
Seed microsphere suspended dispersed solution 2-4g/L Han polystyrene microsphere, it is preferred that polystyrene seed is micro-
Ball suspended dispersed solution 2.5g/L Han polystyrene microsphere.And for example, polystyrene seed microsphere suspended dispersed
In solution, polystyrene microsphere is identical with Sodium Dodecyl Sulfate, so, is conducive to point
Dissipate property preferable polystyrene seed microsphere suspended dispersed solution.
Preferably, by ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) methanol and thionyl chloride
Reaction, obtains ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) chloromethanes；Such as, both
Under room temperature or room temperature react, the response time is 1 to 3 hour, the productivity of reaction up to 100% or
Person approximates 100%.And for example, by chloro-for 1-2-(dichloro (benzene) methyl) benzene, styrene and aluminum chloride
Reaction, is subsequently adding water stopped reaction, then is extracted with ethyl acetate, afterwards by ethyl acetate layer with full
And brine It, anhydrous sodium sulfate is dried, and 50 DEG C of decompression rotary evaporations, to residual liquid, stop
Rotation is steamed, and stands, and separates out ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) methanol；Such as use
Ethyl acetate extracts at least twice, and for example, is extracted with ethyl acetate repeatedly；Such as, by chloro-for 1-2-(two
Chlorine (benzene) methyl) benzene and styrene puts in reaction bulb, and it is subsequently adding aluminum chloride and reacts,
Reacting under room temperature or room temperature, the response time is 2 to 5 hours, and the productivity of reaction can be more than 80%；
And for example, rotation is steamed to residual liquid less than 180mL, 150mL or 120mL etc., and and for example, rotation is steamed extremely
Residual liquid starts naked eyes visible solid state etc. occur.Preferably, by neighbour's chlorobenzophenone and phosphorus pentachloride
Join in reaction bulb, mechanical agitation, it is warming up to 135 DEG C and reacts, reaction adds frozen water after terminating,
Separatory after stirring；Lower floor's liquid frozen water cleans, it is preferred that cleans repeatedly with frozen water, obtains 1-chlorine
-2-(dichloro (benzene) methyl) benzene；Such as, by adjacent chlorobenzophenone and the phosphorus pentachloride of equimolar amounts
Join in reaction bulb, mechanical agitation, it is warming up to 135 DEG C, reacts 1 to 3 hour, question response terminates
After, add frozen water, stir 5min, separatory；Lower floor's liquid frozen water cleans twice again, obtains 1-chlorine
-2-(dichloro (benzene) methyl) benzene, the productivity of reaction can be more than 90%.
Preferably, described preparation method comprises the following steps: preparation polystyrene polymeric microsphere reaction
The aqueous phase solution of system, wherein contains polyvinyl alcohol 10g/L, containing sodium lauryl sulphate 2.5g/L；Take portion
Divide described aqueous phase solution, by the polystyrene microsphere suspended dispersed of monodispersed 25 μm uniform particle diameter in water
In phase solution, the wherein 2.5g/L Han polystyrene microsphere, obtain polystyrene seed microsphere suspended dispersed molten
Liquid；Benzoyl peroxide is dissolved in containing styrene monomer, ((2 '-chloro-phenyl)-(4 '-vinyl benzene
Base)-phenyl) in chloromethanes, and the mixed liquor of divinylbenzene, obtain oily solution, wherein,
The mass percent of benzoyl peroxide is 0.9% to 1.1%；Such as, the quality hundred of benzoyl peroxide
Proportion by subtraction is 1%；Preferably, the mass percent of benzoyl peroxide and described mixed liquor be 0.98% to
0.99%:1；And for example, benzoyl peroxide mass percent in oily solution is 0.95% to 1%.
Separately take the described aqueous phase solution of part, described oily solution is joined in aqueous phase solution, obtain profit two
The mixed system being layered mutually, ultrasonic mixing makes emulsion, wherein, scattered oiliness droplet diameter
Less than 1 μm.Preferably, when preparing emulsion, oily solution is 1:(1 with the ratio of aqueous phase solution
To 5), it is preferred that the volume ratio of water-oil phase is 1:(1.8 to 4.2), and for example, oily solution and water
The ratio of phase solution is 1:(1.5 to 2.5).Then, by polystyrene seed microsphere suspended dispersed solution
Join described emulsion, be placed in 20 DEG C to 45 DEG C oil baths, it is preferred that at nitrogen or noble gas
Protection under, be placed in 20 DEG C to 45 DEG C oil baths；In view of realizing cost, preferably nitrogen.Such as, put
In 25 DEG C to 40 DEG C oil baths, it is preferred that be placed in 28 DEG C to 32 DEG C oil baths；Preferably, described oil bath
Temperature be 30 DEG C；And under mechanical agitation swelling 15 to 30 hours, such as, stir at machinery
Mix under effect swelling 15,18,21,22,25,28 or 30 hours；And for example, churned mechanically turn
Speed is 100 to 200 revs/min, and such as, churned mechanically rotating speed is 120 to 180 revs/min；Preferably,
Churned mechanically rotating speed is 140 to 160 revs/min；Then, it is warmed up to 66 DEG C to 82 DEG C and keeps machinery
Stirring carries out polyreaction 20 to 32 hours, such as, is warmed up to 72 DEG C to 78 DEG C, and for example, heats up
To 75 DEG C or 76 DEG C；And for example, churned mechanically rotating speed is kept to be 120 to 180 revs/min；Preferably,
Churned mechanically rotating speed is 140 to 160 revs/min；Preferably, mechanical agitation time swelling with when being polymerized
Mechanical agitation, both rotating speeds are identical；Such as, described mechanical agitation rotating speed is 150rpm, at machinery
Under stirring action, swelling time is 18 hours, is warmed up to 75 DEG C and keeps mechanical agitation to carry out polyreaction
24 hours；Then, with lauryl sodium sulfate aqueous solution gravitational settling classification, the poly-of small particle is removed
Phenylethylene micro ball, obtains the 2-chlorine trityl group chlorine microsphere of uniform particle diameter.Preferably, dodecane is used
Repeatedly, such removal effect is preferable in base aqueous sodium persulfate solution gravitational settling classification.Preferably, obtain
The lauryl sodium sulfate aqueous solution 500mL gravitational settling classification of product 2.5g/L 3 times, removes micro-
A small amount of polystyrene microsphere of small particle, obtains the 2-chlorine trityl group chlorine resin microsphere of uniform particle diameter.
Such as, the preparation method of a kind of 2-chlorine trityl group chlorine resin, it comprises the following steps.
1, prepared by PS seed, and dispersed polymeres prepares 4.5 μm uniform particle diameter PS microspheres, swelling
Styrene, is polymerized again, obtains 25 μm uniform particle diameter PS microspheres, and this PS microsphere closes as solid phase
The seed of resin microsphere.
2, prepared by monomer
Each monomer and preparation flow are as in figure 2 it is shown, adjacent chlorobenzophenone (1) and phosphorus pentachloride (2)
The synthesis chloro-2-of 1-(dichloro (benzene) methyl) benzene (3), itself and styrene (4), aluminum chloride (5)
Synthesis ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) methanol (6), then with thionyl chloride
(7) reaction obtains ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) chloromethanes.It is correlated with
Synthetic method and reaction condition can use prior art to realize, and under different material ratio, can obtain
Product, the present invention does not claim concrete method for preparing monomer, but for whole preparation flow and
Its follow-up preparation method preparing 2-chlorine trityl group chlorine resin, belongs to the claimed model of the present invention
Enclose.In each monomer and preparation flow, it is preferred that a kind of raw material is the most excessive, so, produce final
The yield ratio of thing is advantageous.Such as, adjacent chlorobenzophenone is The more the better, but increases cost too much, 1
Equivalent is to react more preferably to select.
3, solid phase synthesis resin-made is standby
2-chlorine triphenyl with the band double bond of the PS seed swelling different proportion prepared by above-mentioned steps 1
Methyl chloride monomer, styrene, divinylbenzene, with BPO (Benzoyl peroxide, benzoyl peroxide
Formyl) it is initiator, PVA (polyvinyl alcohol) is stabilizer, and SDS (sodium lauryl sulphate) is
Emulsifying agent, prepares the trityl group chlorine solid phase synthesis resin microsphere of 80 to 120 μm, microsphere
Clean with acetone and/or methanol, dry, complete to produce.
Such as, microsphere cleaning step is as follows: the microsphere after 100g staged care, first with 500mL third
Ketone cleans one time, sucking filtration；Add 500mL methanol to clean one time, sucking filtration；Repeat with acetone,
Methanol cleans, and repeats procedure above three times.Product 12h at 60 DEG C is dried, and directly packs, as
Product.
The preparation method of PS seed is exemplified below.
Such as, prepared by the polystyrene microsphere of 4.5 μm uniform particle diameter, detailed process is as follows: 290mg
Radical initiator azodiisobutyronitrile (AIBN) is dissolved in 8mL (7.248g) styrene (Styrene)
In monomer, the mass percent making AIBN account for styrene monomer is 4%.0.624g polyvinylpyrrolidine
Ketone (PVP) and 0.6g Triton X-100 (0.572mL) are dissolved in 32mL dehydrated alcohol, by 8mL
Styrene monomer solution dissolved with azodiisobutyronitrile joins in above-mentioned ethanol solution so that
In whole mixed solution the concentration of polyvinylpyrrolidone and Triton X-100 be respectively 15.6g/L and
15.0g/L, it is 20% that styrene monomer accounts for the percent by volume of whole solution.Under nitrogen protection, will
Above-mentioned mixed solution stirs 30min with the mechanical agitation speed of 150rpm., then will fill above-mentioned mixed
The three neck round bottom flask closing solution is placed in the oil bath that temperature is 70 DEG C, mechanical agitation speed is adjusted to
24h is reacted after 100rpm.React product monodisperse polystyrene (PS) polymer microsphere after terminating
With absolute ethanol washing 3-5 time, obtain the polystyrene microsphere of 4.5 μm uniform particle diameter.
And for example, 25 μm uniform particle diameter polystyrene microsphere preparations are as follows:
1, preparation (PVA) Han polyvinyl alcohol is 10g/L and (SDS) Han sodium lauryl sulphate is
The aqueous solution 1L of 2.5g/L is as the aqueous phase solution preparing polystyrene polymeric microsphere reaction system.
2, by the polystyrene microsphere suspended dispersed of 0.4g single dispersing 4.5 μm uniform particle diameter in 20mL
In the above-mentioned aqueous solution containing 10g/L PVA and 2.5g/L SDS, obtain the suspension point of PS seed microsphere
Dissipate solution.
3,857mg radical initiator azodiisobutyronitrile (AIBN) is dissolved in containing 85.7g (86.6
ML), in styrene monomer, it is 1% that radical initiator accounts for the mass percent of high molecular polymerization monomer.
The oily solution obtained is joined in the aqueous solution that 173mL contains 10g/L PVA and 2.5g/L SDS,
Obtaining the mixed system of water-oil phase layering, wherein, the volume ratio of water-oil phase is 1:2.By ultrasonic
The mixed system that this water-oil phase is layered is made emulsion by effect, and the ultrasonic power used is 300W,
Ultrasonic time is 9s, and interval time is 3s, and number of repetition is 90 times, observes under an optical microscope
In final emulsion, scattered oiliness droplet diameter is less than 1 μm.
4,20mL polystyrene seed microsphere aaerosol solution is joined in above-mentioned emulsion, this is molten
Swollen mixture system is placed in 30 DEG C of oil baths, swelling 18h under the mechanical agitation of 150rpm,
After polystyrene seed microsphere absorbs the oiliness droplet in emulsion, diameter dimension increases.To polyphenyl second
After alkene seed microsphere absorbs the oiliness droplet in overwhelming majority emulsion, temperature is risen to 70 DEG C, protect
Hold mixing speed polyreaction 24h, the product 25 μm uniform particle diameter polystyrene microsphere obtained, and
A small amount of polystyrene microsphere less than 1 μm particle diameter, with the aqueous solution 500mL gravity of 2.5g/L SDS
Classification of sedimentation removes the polystyrene microsphere of 1 μm particle diameter for 3 times, obtains the polyphenyl of 25 μm uniform particle diameter
Ethylene microsphere seed.
Continuing with the reaction and the preparation method of the most each monomer illustrated in Fig. 2, these are single
Body can also use additive method to realize.
Prepared by compound 3 (the chloro-2-of 1-(dichloro (benzene) methyl) benzene): 100g neighbour's chlorobenzophenone
(1) with 97g phosphorus pentachloride (2) 1eq, join in 500mL reaction bulb, mechanical agitation, heats up
To 135 DEG C, react 2h.After reaction terminates, add 200mL frozen water, stir 5min, separatory；Under
Layer liquid 200mL frozen water cleans twice again.Obtaining 113g compound 3, productivity is about 90%.
Prepared by compound 6 ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) methanol: 100g
Compound 3 and 76.8g styrene (4) 2eq, add in 500mL reaction bulb, then add 98g trichlorine
Change aluminum (5) 2eq, room temperature reaction 3h.After reaction terminates, add 100g water stopped reaction, then use
300mL ethyl acetate extracts three times, and ethyl acetate layer saturated aqueous common salt washs one time, anhydrous slufuric acid
Sodium is dried 12h.50 DEG C of decompression rotary evaporations, to residual 150mL liquid, stop rotation and steam, stand, analysis
Going out 94.5g product 6, productivity is about 80%.
Prepared by compound 8 ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) chloromethanes: 100g
Compound 6 and 74.3g thionyl chloride (7) 2eq, room temperature reaction 2h, obtain product 8, and productivity is about
100%.
Solid phase synthesis resin-made is standby as it is shown on figure 3, such as, PS seed swelling prepared by method described above
The 2-chlorine trityl group chlorine monomer of different proportion, styrene, divinylbenzene, with BPO for causing
Agent, PVA is stabilizer, and SDS is emulsifying agent, prepares the trityl group chlorine of 80-120 μm
Solid phase synthesis resin microsphere.Microsphere acetone, dichloromethane clean, and dry, and complete to produce, aobvious
Photograph under micro mirror as shown in Figure 4, from this photograph, the 2-chlorine triphen obtained by this preparation method
Ylmethyl chlorine resin microsphere uniform particle diameter is the best.Further, after tested, this solid phase synthesis tree is used
Fat, polyreaction yield is up to 80%-100%.
Provide some embodiments the most again and contrast, 2-chlorine trityl group of the present invention is described
The preparation method of chlorine resin.
Preparation is 10g/L containing PVA and is that the aqueous solution 10L of 2.5g/L is as preparing polyphenyl second containing SDS
The aqueous phase solution of alkene polymer microsphere reaction system.
By the polystyrene microsphere suspended dispersed containing 1.05g single dispersing 25 μm uniform particle diameter in 420mL
In above-mentioned aqueous phase solution, obtain PS seed microsphere suspended dispersed solution.
Further, 1.18g BPO is dissolved in containing 60g styrene monomer, 60g compound 8,1.2g80%
In divinylbenzene, the oily solution obtained is joined in the above-mentioned aqueous phase solution of 250mL, obtain oil
The mixed system of water two phase stratification.By ultrasonication, the mixed system that this water-oil phase is layered is made
Emulsion, the ultrasonic power used is 470W, and ultrasonic time is 10s, and interval time is 2.5s,
Number of repetition is 95 times, and oiliness droplet diameter is less than 1 μm.
Above-mentioned 420mL polystyrene seed microsphere aaerosol solution is joined in above-mentioned emulsion, should
Swollen mixt system is placed in oil bath, prepares 2-chlorine trityl group chlorine resin by following reaction condition
Microsphere is as shown in table 1 below.
Table 1
It is further continued for illustrating the preparation method of 2-chlorine trityl group chlorine resin of the present invention below,
Including the preparation method of 2-chlorine trityl group chlorine resin microsphere, with these 2-chlorine trityl group chlorine trees
Lipoid microsphere, can prepare 2-chlorine trityl group chlorine resin.
It should be noted that for the ease of test comparison, below each example have employed many identical realities
Testing condition, these identical experiment conditions are not as the claimed model of preparation method for the present invention
The extra restriction enclosed, and as just example therein, for illustrate the present invention preparation method and
The 2-chlorine trityl group chlorine resin microsphere prepared.
Example 1 carrying capacity 0.295mmol/g, the 2-chlorine trityl group chlorine resin of 100 μm uniform particle diameter
Prepared by microsphere:
1, preparation (PVA) Han polyvinyl alcohol is 10g/L and (SDS) Han sodium lauryl sulphate is
The aqueous solution 10L of 2.5g/L is as the aqueous phase solution preparing polystyrene polymeric microsphere reaction system.
2, by the polystyrene microsphere suspended dispersed containing 1g single dispersing 25 μm uniform particle diameter in 400mL
In the above-mentioned aqueous solution containing 10g/L PVA and 2.5g/L SDS, obtain PS seed microsphere suspended dispersed
Solution.
3,0.8g benzoyl peroxide (BPO) is dissolved in containing 72g styrene monomer, 8g chemical combination
Thing 8, in 1g80% divinylbenzene, radical initiator accounts for the mass percent of high molecular polymerization monomer
It is 1%.The oily solution obtained is joined 165mL and contains 10g/L PVA's and 2.5g/L SDS
In aqueous solution, obtaining the mixed system of water-oil phase layering, wherein, the volume ratio of water-oil phase is about
1:2.By ultrasonication, the mixed system that this water-oil phase is layered being made emulsion, used is super
Acoustical power is 500W, and ultrasonic time is 9s, and interval time is 3s, and number of repetition is 90 times, at light
Learn scattered oiliness droplet diameter in the emulsion that basis of microscopic observation is final and be less than 1 μm.
4,400mL polystyrene seed microsphere aaerosol solution is joined in above-mentioned emulsion, this is molten
Swollen mixture system is placed in 30 DEG C of oil baths, swelling 18h under the mechanical agitation of 150rpm, poly-
After styrene seed microsphere absorbs the oiliness droplet in emulsion, diameter dimension increases.To polystyrene
After seed microsphere absorbs the oiliness droplet in overwhelming majority emulsion, temperature is risen to 75 DEG C, keep
Mixing speed polyreaction 24h, the product 100 μm uniform particle diameter obtained gathering containing 10% compound 8
Phenylethylene micro ball, and a small amount of polystyrene microsphere less than 1 μm particle diameter, water-soluble with 2.5g/L SDS
The polystyrene microsphere of 1 μm particle diameter is removed in liquid 500mL gravitational settling classification for 3 times, and obtaining particle diameter is
100 μm, carrying capacity 0.295mmol/g, the 2-chlorine trityl group chlorine resin of the uniform particle diameter of 1% degree of cross linking
Microsphere.
Example 2 carrying capacity 0.59mmol/g, the 2-chlorine trityl group chlorine resin of 100 μm uniform particle diameter
Prepared by microsphere:
1, preparation (PVA) Han polyvinyl alcohol is 10g/L and (SDS) Han sodium lauryl sulphate is
The aqueous solution 10L of 2.5g/L is as the aqueous phase solution preparing polystyrene polymeric microsphere reaction system.
2, by the polystyrene microsphere suspended dispersed containing 1g single dispersing 25 μm uniform particle diameter in 400mL
In the above-mentioned aqueous solution containing 10g/L PVA and 2.5g/L SDS, obtain PS seed microsphere suspended dispersed
Solution.
3,0.8g benzoyl peroxide (BPO) is dissolved in containing 64g styrene monomer, 16g chemical combination
Thing 8, in 1g80% divinylbenzene, radical initiator accounts for the mass percent of high molecular polymerization monomer
It is 1%.The oily solution obtained is joined 165mL and contains 10g/L PVA's and 2.5g/L SDS
In aqueous solution, obtaining the mixed system of water-oil phase layering, wherein, the volume ratio of water-oil phase is about
1:2.By ultrasonication, the mixed system that this water-oil phase is layered being made emulsion, used is super
Acoustical power is 500W, and ultrasonic time is 9s, and interval time is 3s, and number of repetition is 90 times, at light
Learn scattered oiliness droplet diameter in the emulsion that basis of microscopic observation is final and be less than 1 μm.
4,400mL polystyrene seed microsphere aaerosol solution is joined in above-mentioned emulsion, this is molten
Swollen mixture system is placed in 30 DEG C of oil baths, swelling 18h under the mechanical agitation of 150rpm, poly-
After styrene seed microsphere absorbs the oiliness droplet in emulsion, diameter dimension increases.To polystyrene
After seed microsphere absorbs the oiliness droplet in overwhelming majority emulsion, temperature is risen to 75 DEG C, keep
Mixing speed polyreaction 24h, the product 100 μm uniform particle diameter obtained gathering containing 20% compound 8
Phenylethylene micro ball, and a small amount of polystyrene microsphere less than 1 μm particle diameter, water-soluble with 2.5g/L SDS
The polystyrene microsphere of 1 μm particle diameter is removed in liquid 500mL gravitational settling classification for 3 times, and obtaining particle diameter is
100 μm, carrying capacity 0.67mmol/g, the 2-chlorine trityl group chlorine resin of the uniform particle diameter of 1% degree of cross linking
Microsphere.
Example 3 carrying capacity 1.18mmol/g, the 2-chlorine trityl group chlorine resin of 100 μm uniform particle diameter
Prepared by microsphere:
1, preparation (PVA) Han polyvinyl alcohol is 10g/L and (SDS) Han sodium lauryl sulphate is
The aqueous solution 10L of 2.5g/L is as the aqueous phase solution preparing polystyrene polymeric microsphere reaction system.
2, by the polystyrene microsphere suspended dispersed containing 1g single dispersing 25 μm uniform particle diameter in 400mL
In the above-mentioned aqueous solution containing 10g/L PVA and 2.5g/L SDS, obtain PS seed microsphere suspended dispersed
Solution.
3,0.8g benzoyl peroxide (BPO) is dissolved in containing 48g styrene monomer, 32g chemical combination
Thing 8, in 1g80% divinylbenzene, radical initiator accounts for the mass percent of high molecular polymerization monomer
It is 1%.The oily solution obtained is joined 165mL and contains 10g/L PVA's and 2.5g/L SDS
In aqueous solution, obtaining the mixed system of water-oil phase layering, wherein, the volume ratio of water-oil phase is about
1:2.By ultrasonication, the mixed system that this water-oil phase is layered being made emulsion, used is super
Acoustical power is 500W, and ultrasonic time is 9s, and interval time is 3s, and number of repetition is 90 times, at light
Learn scattered oiliness droplet diameter in the emulsion that basis of microscopic observation is final and be less than 1 μm.
4,400mL polystyrene seed microsphere aaerosol solution is joined in above-mentioned emulsion, this is molten
Swollen mixture system is placed in 30 DEG C of oil baths, swelling 18h under the mechanical agitation of 150rpm, poly-
After styrene seed microsphere absorbs the oiliness droplet in emulsion, diameter dimension increases.To polystyrene
After seed microsphere absorbs the oiliness droplet in overwhelming majority emulsion, temperature is risen to 75 DEG C, keep
Mixing speed polyreaction 24h, the product 100 μm uniform particle diameter obtained gathering containing 40% compound 8
Phenylethylene micro ball, and a small amount of polystyrene microsphere less than 1 μm particle diameter, water-soluble with 2.5g/L SDS
The polystyrene microsphere of 1 μm particle diameter is removed in liquid 500mL gravitational settling classification for 3 times, and obtaining particle diameter is
100 μm, carrying capacity 1.18mmol/g, the 2-chlorine trityl group chlorine resin of the uniform particle diameter of 1% degree of cross linking
Microsphere.
Example 4 carrying capacity 1.18mmol/g, the 2-chlorine trityl group chlorine resin of 80 μm uniform particle diameter is micro-
Prepared by ball:
1, preparation (PVA) Han polyvinyl alcohol is 10g/L and (SDS) Han sodium lauryl sulphate is
The aqueous solution 10L of 2.5g/L is as the aqueous phase solution preparing polystyrene polymeric microsphere reaction system.
2, by the polystyrene microsphere suspended dispersed containing 1g single dispersing 25 μm uniform particle diameter in 400mL
In the above-mentioned aqueous solution containing 10g/L PVA and 2.5g/L SDS, obtain PS seed microsphere suspended dispersed
Solution.
3,0.4g benzoyl peroxide (BPO) is dissolved in containing 24g styrene monomer, 16g chemical combination
Thing 8, in 0.5g80% divinylbenzene, radical initiator accounts for the percent mass of high molecular polymerization monomer
Ratio is 1%.The oily solution obtained is joined 165mL and contains 10g/L PVA and 2.5g/L SDS
Aqueous solution in, obtain water-oil phase layering mixed system, wherein, the volume ratio of water-oil phase is about
For 1:4.By ultrasonication, the mixed system that this water-oil phase is layered is made emulsion, used
Ultrasonic power is 500W, and ultrasonic time is 9s, and interval time is 3s, and number of repetition is 90 times,
In the emulsion that optical microphotograph Microscopic observation is final, scattered oiliness droplet diameter is less than 1 μm.
4,400mL polystyrene seed microsphere aaerosol solution is joined in above-mentioned emulsion, this is molten
Swollen mixture system is placed in 30 DEG C of oil baths, swelling 18h under the mechanical agitation of 150rpm, poly-
After styrene seed microsphere absorbs the oiliness droplet in emulsion, diameter dimension increases.To polystyrene
After seed microsphere absorbs the oiliness droplet in overwhelming majority emulsion, temperature is risen to 75 DEG C, keep
Mixing speed polyreaction 24h, the product 100 μm uniform particle diameter obtained gathering containing 40% compound 8
Phenylethylene micro ball, and a small amount of polystyrene microsphere less than 1 μm particle diameter, water-soluble with 2.5g/L SDS
The polystyrene microsphere of 1 μm particle diameter is removed in liquid 500mL gravitational settling classification for 3 times, and obtaining particle diameter is
80 μm, carrying capacity 1.18mmol/g, the 2-chlorine trityl group chlorine resin of the uniform particle diameter of 1% degree of cross linking is micro-
Ball.
Example 5 carrying capacity 1.18mmol/g, the 2-chlorine trityl group chlorine resin of 120 μm uniform particle diameter
Prepared by microsphere:
1, preparation (PVA) Han polyvinyl alcohol is 10g/L and (SDS) Han sodium lauryl sulphate is
The aqueous solution 10L of 2.5g/L is as the aqueous phase solution preparing polystyrene polymeric microsphere reaction system.
2, by the polystyrene microsphere suspended dispersed containing 1g single dispersing 25 μm uniform particle diameter in 400mL
In the above-mentioned aqueous solution containing 10g/L PVA and 2.5g/L SDS, obtain PS seed microsphere suspended dispersed
Solution.
3,1.4g benzoyl peroxide (BPO) is dissolved in containing 84g styrene monomer, 56g chemical combination
Thing 8, in 1.75g80% divinylbenzene, radical initiator accounts for the quality hundred of high molecular polymerization monomer
Proportion by subtraction is 1%.The oily solution obtained is joined 280mL and contains 10g/L PVA and 2.5g/L SDS
Aqueous solution in, obtain water-oil phase layering mixed system, wherein, the volume ratio of water-oil phase is about
For 1:2.By ultrasonication, the mixed system that this water-oil phase is layered is made emulsion, used
Ultrasonic power is 500W, and ultrasonic time is 9s, and interval time is 3s, and number of repetition is 90 times,
In the emulsion that optical microphotograph Microscopic observation is final, scattered oiliness droplet diameter is less than 1 μm.
4,400mL polystyrene seed microsphere aaerosol solution is joined in above-mentioned emulsion, this is molten
Swollen mixture system is placed in 30 DEG C of oil baths, swelling 18h under the mechanical agitation of 150rpm, poly-
After styrene seed microsphere absorbs the oiliness droplet in emulsion, diameter dimension increases.To polystyrene
After seed microsphere absorbs the oiliness droplet in overwhelming majority emulsion, temperature is risen to 75 DEG C, keep
Mixing speed polyreaction 24h, the product 100 μm uniform particle diameter obtained gathering containing 40% compound 8
Phenylethylene micro ball, and a small amount of polystyrene microsphere less than 1 μm particle diameter, water-soluble with 2.5g/L SDS
The polystyrene microsphere of 1 μm particle diameter is removed in liquid 500mL gravitational settling classification for 3 times, and obtaining particle diameter is
120 μm, carrying capacity 1.18mmol/g, the 2-chlorine trityl group chlorine resin of the uniform particle diameter of 1% degree of cross linking
Microsphere.
Further, embodiments of the invention also include, each technical characteristic of the various embodiments described above, phase
The preparation method of the 2-chlorine trityl group chlorine resin that combination is formed mutually.
It should be noted that the description of the present invention and accompanying drawing thereof give the most real of the present invention
Execute example, but, the present invention can be realized by many different forms, however it is not limited to this specification
Described embodiment, these embodiments are not as the extra restriction to present invention, it is provided that these
The purpose of embodiment is to make the understanding to the disclosure more thorough comprehensively.Further, above-mentioned
Each technical characteristic continues to be mutually combined, and forms various embodiments the most enumerated above, is accordingly to be regarded as this
Speak frankly the scope that bright secretary carries；Further, for those of ordinary skills, can basis
Described above is improved or is converted, and all these modifications and variations all should belong to the appended power of the present invention
The protection domain that profit requires.
Claims (10)
1. the preparation method of a 2-chlorine trityl group chlorine resin, it is characterised in that include following
Step:
Use the 2-chlorine trityl group chlorine monomer of band double bond, styrene and the swelling polyphenyl of divinylbenzene
Ethylene microsphere seed, with benzoyl peroxide as initiator, polyvinyl alcohol is stabilizer, dodecyl
Sodium sulfate is emulsifying agent, prepares 2-chlorine trityl group chlorine resin microsphere.
Preparation method the most according to claim 1, it is characterised in that prepare 2-chlorine triphen
After ylmethyl chlorine resin microsphere, described microsphere is carried out, then dries.
Preparation method the most according to claim 2, it is characterised in that the 2-of described band double bond
Chlorine trityl group chlorine monomer is ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) chloromethanes.
Preparation method the most according to claim 3, it is characterised in that by ((2 '-chloro-phenyl)
-(4 '-ethenylphenyl)-phenyl) methanol reacts with thionyl chloride, obtain ((2 '-chloro-phenyl)-(4 '-
Ethenylphenyl)-phenyl) chloromethanes.
Preparation method the most according to claim 4, it is characterised in that by chloro-for 1-2-(dichloro (benzene)
Methyl) benzene, styrene reacts with aluminum chloride, is subsequently adding water stopped reaction, then uses ethyl acetate
Extraction, washs ethyl acetate layer saturated aqueous common salt afterwards, and anhydrous sodium sulfate is dried, and 50 DEG C subtract
Pressure rotary evaporation, to residual liquid, stops rotation and steams, stand, separate out ((2 '-chloro-phenyl)-(4 '-ethylene
Base phenyl)-phenyl) methanol.
Preparation method the most according to claim 5, it is characterised in that by neighbour's chlorobenzophenone with
Phosphorus pentachloride joins in reaction bulb, mechanical agitation, is warming up to 135 DEG C and reacts, after reaction terminates
Add frozen water, separatory after stirring；Lower floor's liquid frozen water cleans, and obtains the chloro-2-of 1-(dichloro (benzene)
Methyl) benzene.
Preparation method the most according to claim 1, it is characterised in that described polystyrene microsphere
Seed is 25 μm polystyrene microspheres of uniform particle diameter.
8. according to preparation method according to any one of claim 1 to 7, it is characterised in that include
Following steps:
Preparation polystyrene polymeric microsphere reaction system aqueous phase solution, wherein containing polyvinyl alcohol 10g/L,
Containing sodium lauryl sulphate 2.5g/L；
Take the described aqueous phase solution of part, the polystyrene microsphere of monodispersed 25 μm uniform particle diameter is suspended
It is scattered in aqueous phase solution, wherein the 2.5g/L Han polystyrene microsphere, obtains polystyrene seed microsphere and hang
Floating dispersion soln；
Benzoyl peroxide is dissolved in containing ((2 '-chloro-phenyl)-(4 '-ethenylphenyl)-phenyl) chlorine
Methane, in styrene monomer, and the mixed liquor of divinylbenzene, obtains oily solution, wherein,
The mass percent of benzoyl peroxide is 0.9% to 1.1%；
Separately take the described aqueous phase solution of part, described oily solution is joined in aqueous phase solution, obtains oil
The mixed system of water two phase stratification, ultrasonic mixing makes emulsion, wherein, scattered oiliness droplet
Diameter is less than 1 μm；
Polystyrene seed microsphere suspended dispersed solution is joined described emulsion, is placed in 20 DEG C to 45 DEG C
Oil bath, under mechanical agitation after swelling 15 to 30 hours, is warmed up to 66 DEG C and to 82 DEG C and keeps
Mechanical agitation carries out polyreaction 20 to 32 hours, uses lauryl sodium sulfate aqueous solution gravitational settling
Classification, removes the polystyrene microsphere of small particle, obtains the 2-chlorine trityl group chlorine tree of uniform particle diameter
Lipoid microsphere.
Preparation method the most according to claim 8, it is characterised in that benzoyl peroxide and institute
The mass percent stating mixed liquor is 0.98% to 0.99%:1；In the mixed system of water-oil phase layering,
The volume ratio of water-oil phase is 1:(1.8 to 4.2)；The temperature of described oil bath is 30 DEG C；Described machinery stirs
Mixing rotating speed is 150rpm, and under mechanical agitation, swelling time is 18 hours, is warmed up to 75 DEG C also
Mechanical agitation is kept to carry out polyreaction 24 hours, the lauryl sulphate acid of the product 2.5g/L obtained
Sodium water solution 500mL gravitational settling classification 3 times, removes a small amount of polystyrene microsphere of nominal particle size,
Obtain the 2-chlorine trityl group chlorine resin microsphere of uniform particle diameter.
Preparation method the most according to claim 9, it is characterised in that further comprise the steps of: employing
Described 2-chlorine trityl group chlorine resin microsphere prepares 2-chlorine trityl group chlorine resin.
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| CN101838355A (en) * | 2009-03-20 | 2010-09-22 | 中国科学院过程工程研究所 | Preparation method of 2-chloro trityl chloride resin |
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