CN102924638B - Preparation method of double-end sulfhydryl polymer - Google Patents
Preparation method of double-end sulfhydryl polymer Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920000642 polymer Polymers 0.000 title claims abstract description 11
- 125000003396 thiol group Chemical group [H]S* 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003999 initiator Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002798 polar solvent Substances 0.000 claims abstract description 12
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004440 column chromatography Methods 0.000 claims abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- -1 tripropyl chlorine silicon Chemical compound 0.000 claims description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229920013730 reactive polymer Polymers 0.000 claims description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002460 imidazoles Chemical group 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 claims description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- PLMNEJBJFZHNGF-UHFFFAOYSA-N 3-bromopropane-1-thiol Chemical compound SCCCBr PLMNEJBJFZHNGF-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims description 4
- BVUDMJXNWXLNSN-UHFFFAOYSA-N 3-chloro-2-methylpropane-1-thiol Chemical compound SCC(C)CCl BVUDMJXNWXLNSN-UHFFFAOYSA-N 0.000 claims description 3
- TZCFWOHAWRIQGF-UHFFFAOYSA-N 3-chloropropane-1-thiol Chemical compound SCCCCl TZCFWOHAWRIQGF-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical group C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- MHYGQXWCZAYSLJ-UHFFFAOYSA-N tert-butyl-chloro-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C(C)(C)C)C1=CC=CC=C1 MHYGQXWCZAYSLJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001730 thiiranyl group Chemical group 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 2
- 241000786137 Halogeton glomeratus Species 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000007306 functionalization reaction Methods 0.000 abstract 1
- 125000002883 imidazolyl group Chemical group 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 44
- 229910052786 argon Inorganic materials 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 10
- 238000013019 agitation Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920001195 polyisoprene Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920000359 diblock copolymer Polymers 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 101000777220 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 3 Proteins 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 102100031287 Ubiquitin carboxyl-terminal hydrolase 3 Human genes 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920005601 base polymer Polymers 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 229910052801 chlorine Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
The invention relates to a preparation method of a double-end sulfhydryl polymer; reacting a mercapto-group protection reagent and halogeton mercaptan in a molar ratio of 1: 1 in a polar solvent at a reaction temperature of-5 ℃ for 24 hours, extracting with a weak polar solvent, taking supernatant, evaporating the solvent on a rotary evaporator, and separating by using column chromatography to obtain an initiator intermediate; the catalyst is imidazole, pyrimidine or pyridine; reacting the initiator intermediate with metal lithium in a nonpolar solvent according to the molar weight of 1: 6.7, wherein the reaction temperature is 30-70 ℃ to obtain the initiator; adding a solvent, an initiator, a monomer and a structure regulator into a reaction kettle in sequence for reaction to obtain an active polymer, wherein the reaction temperature is 0-60 ℃; adding an end-capping reagent into the polymer for reaction, and adding methanol for termination; acidifying the terminated polymer with inorganic acid to obtain a double-end sulfhydryl polymer; the obtained polymer has narrow molecular weight distribution, controllable molecular weight, adjustable chain microstructure and high functionalization efficiency.
Description
Technical field
The invention belongs to field prepared by end functionalized polymer, relate to a kind of preparation method of both-end sulfydryl polymkeric substance, adopt the initiator trigger monomer polymerization of protected silane sulfydryl to prepare both-end sulfydryl polymkeric substance.
Background technology
End functionalized polymer is that a kind of molecular backbone chain end is with the polymkeric substance of active group, low-molecular-weight both-end sulfydryl polyhutadiene or polyisoprene are a kind of fluid rubbers, due to its special active end group and the liquid performance of normal temperature, make it have the special purpose that solid rubber cannot be compared.For example both-end sulfydryl polyhutadiene is because its special sulfydryl makes it faster than two hydroxy-terminated polybutadienes curing speeds at normal temperatures, so successfully for the aspects such as tackiness agent of ca(u)lk material, sealing material and solid rocket propellant, US4 for example, 100,418 have announced a kind of sealing material based on both-end sulfydryl polyhutadiene, and this material has good storage stability.
The preparation method of both-end sulfydryl polymkeric substance mainly contains end group conversion method and anionic polymerization.
End group conversion method reacts to prepare by end group by the polymkeric substance with terminal hydroxy group or end amido etc.USP3,114,734, USP3,449,301, USP3,547,896 have announced the method that several methods that transform by end group are prepared end sulfydryl polymkeric substance.Although both-end sulfydryl polymkeric substance step prepared by end group conversion method is simple, owing to there being the problem that transformation efficiency is not high in end group conversion process, so remain the material of other functional group in the end sulfydryl polymkeric substance making.On the other hand, because the end functionalized base polymer of liquid is in re-starting end group conversion process, viscosity can increase, so affected its application performance.
At present the anionic polymerisation process of the both-end sulfydryl polymkeric substance of report is mainly organic alkali metal initiator trigger monomer and carries out polymerization, as USP3,240,844 and USP3, the preparation of the end sulfydryl polymkeric substance of mentioning in 755,269, both-end sulfydryl polyhutadiene prepared by the method or both-end sulfydryl isoprene fluid rubber are due in microtexture 1, in 2 structures, content is higher, so the apparent viscosity of polymkeric substance is larger.And in end-blocking process, easily occur pseudo-gels phenomenon, so affected the average functionality of polymkeric substance.
Summary of the invention
The object of this invention is to provide a kind of method of preparing both-end sulfydryl polymkeric substance, the method adopts the anionic initiator trigger monomer polymerization with protected silane sulfydryl, prepares both-end sulfydryl polymkeric substance.
The both-end sulfydryl polymkeric substance the present invention relates to, its general structure is as follows:
R wherein
1, R
2for carbon atom be 1-10 straight-chain paraffin or branched paraffin, R
1, R
2can be identical, also can be different; M is polymerization single polymerization monomer; N is the polymerization degree of monomer, n=10-1000.
Preparation process comprises following several step:
1. initiator intermediate is synthetic
Said initiator intermediate has following general formula:
Pro-S-R-X
Wherein R is that carbon atom is straight-chain paraffin or the branched paraffin of 1-10; X is bromine or chlorine.
Concrete synthetic method is as follows:
Sulfhydryl protected reagent and halogen band mercaptan are dissolved in and are placed in reaction flask in the molar weight ratio of 1: 1, volume is in the polar solvent of 3 times, halo mercaptan, the catalyzer that is in excess in sulfhydryl protected reagent or halogen band mercaptan molar weight 10% is dissolved in the same polar solvent of 2 times of its quality, and splash in reaction flask by constant pressure funnel, temperature of reaction is-5 ℃～5 ℃, 24 hours reaction times, resultant washs three times with 5% sodium hydrogen carbonate solution afterwards, with weak polar solvent, extract, get supernatant liquid and on Rotary Evaporators, boil off solvent, with column chromatography separation, obtain initiator intermediate again,
Said polar solvent has N, dinethylformamide or dimethyl sulfoxide (DMSO);
Sulfhydryl protected reagent used is TERT-BUTYL DIMETHYL CHLORO SILANE, tert-butyl diphenyl chlorosilane, trimethylchlorosilane, chlorotriethyl silane or tripropyl chlorine silicon;
Said halo mercaptan is selected from the chloro-1-sulfur alcohol of 2-, the chloro-1-propylmercaptan of 3-, the bromo-1-sulfur alcohol of 2-, the bromo-1-propylmercaptan of 3-, the chloro-1-butyl sulfhydryl of 4-or 3-chloro-2-methyl-1-propylmercaptan;
Said catalyzer is imidazoles, pyrimidine or pyridine;
Said weak polar solvent sherwood oil or normal hexane;
2. the preparation of initiator
Prepared initiator general formula is as follows:
Pro-S-R-Li
Initiator intermediate in the non-polar solvent of initiator intermediate volume 3 times is reacted is prepared from by molar weight with metallic lithium at 1: 6.7, and initiator intermediate adds in reaction system by constant pressure funnel, and temperature of reaction is 30-70 ℃;
Said non-polar solvent comprises hexanaphthene, normal hexane or benzene, and metallic lithium is that length is the slice of 5-10mm.
(3) reactive polymer is synthetic
Successively solvent, initiator, monomer and structure regulator are added in reactor, wherein solvent volume amount is 4 times of monomer volume, and initiator and structure regulator consumption are respectively: in monomer mass 10g, initiator amount is 0.001～0.01moL; Structure regulator consumption is 0～4 times of monomer volume.After treating monomer reaction, just obtain reactive polymer, temperature of reaction is 0-60 ℃;
Said monomer is divinyl, vinylbenzene or isoprene;
Said solvent is hexanaphthene, normal hexane or benzene;
Said structure regulator is tetrahydrofuran (THF), Tetramethyl Ethylene Diamine or diglyme;
(4) end-blocking of reactive polymer and termination
Equivalent is added after reacting half an hour in reactive polymer and adds methyl alcohol to stop in the capping reagent of initiator molar weight; Or add functionalized terminator reaction 1 hour; Or add coupling agent reaction 1.5 hours; Complete the termination of reactive polymer.
Said capping reagent is thiirane or epithio propane, and functionalized terminator is synthetic initiator intermediate;
Said coupling agent is METHYL TRICHLORO SILANE or tetrachloro silicane;
(5) blocking group removes
By stopping complete polymkeric substance, be dissolved in solvent, 10% the mineral acid acidifying 2 hours with being in excess in initiator amount of substance, has completed removing of blocking group, just obtains pure both-end sulfydryl polymkeric substance by polymers soln is dry afterwards.
Said mineral acid comprises dilute hydrochloric acid, rare nitric acid or dilute sulphuric acid, preferentially selects dilute hydrochloric acid.
The method of preparing end sulfydryl polymkeric substance of comparing current report, this law has advantages of following:
1. adopted the initiator that contains protected silane sulfydryl, this initiator has good solvability in non-polar solvent, therefore can prepare both-end sulfydryl polyhutadiene, both-end sulfydryl polyisoprene and the both-end sulfydryl polystyrene etc. of high Isosorbide-5-Nitrae structural content.In addition, can also in non-polar solvent, add structure regulator, can prepare both-end sulfydryl polyisoprene and the both-end sulfydryl polyhutadiene of different Isosorbide-5-Nitrae structural contents, its Isosorbide-5-Nitrae structural content can regulate between 10% to 90%.
2. because adopt the synthetic both-end sulfydryl polyhutadiene of anionoid polymerization, so the both-end sulfydryl polymkeric substance of preparation has very narrow molecular weight distribution (being less than 1.20), the molecular size range in preparation process easily regulates.
3. can segmentation add monomer, prepare the both-end sulfydryl polymkeric substance of two blocks or many blocks.
Reactive polymer is stopped or the process of end-blocking in all there will not be gelatin phenomenon, resulting polymkeric substance functionality approaches theoretical value.
Based on above advantage of the present invention, we can prepare the both-end sulfydryl polymkeric substance with ordered structure by this anionic initiator that contains protected silane sulfydryl of exploitation, have good prospects for commercial application.
Embodiment
Embodiment 1: the preparation of tertiary butyl dimethyl-silicon sulfenyl propyl chloride
In 250ml there-necked flask, add successively the chloro-1-propylmercaptan of 55.0g (0.5mol) 3-, 75.3g (0.5mol) TERT-BUTYL DIMETHYL CHLORO SILANE, 100mlN, dinethylformamide.Then 37.4g (0.55mol) imidazoles is dissolved in to 40mlN, in dinethylformamide, by constant pressure funnel, splashes in there-necked flask, at 0 ℃, in 1 hour, dropwise, reaction system continues reaction 24 hours.Then with 10% sodium hydrogen carbonate solution, wash 3 times, with petroleum ether extraction, separate petroleum ether layer, on rotatory evaporator, boil off solvent sherwood oil, through chromatographic column separation, obtain intermediate tertiary butyl dimethyl-silicon sulfenyl propyl chloride, productive rate 95%.This reagent is kept in the brown bottle that fills hydrolith.
Embodiment 2: the preparation of tert-butyl diphenyl silicon sulfenyl propyl bromide
In 250ml there-necked flask, add successively the bromo-1-propylmercaptan of 77g (0.5mol) 3-, 137.5g (0.5mol) tert-butyl diphenyl chlorosilane, 100mlN, dinethylformamide.Then 37.4g (0.55mol) imidazoles is dissolved in to 40mlN, in dinethylformamide, by constant pressure funnel, splashes in there-necked flask, at 0 ℃, in 1 hour, dropwise, reaction system continues reaction 24 hours.Sodium hydrogen carbonate solution washing with 10% 3 times, with petroleum ether extraction, separates petroleum ether layer, on rotation musical instruments used in a Buddhist or Taoist mass, boils off solvent sherwood oil, through chromatographic column separation, obtains intermediate tert-butyl diphenyl silicon sulfenyl propyl bromide, productive rate 90%.This reagent is kept in the brown bottle that fills hydrolith.
Embodiment 3: the preparation of triethyl silicon sulfenyl propyl bromide
In 250ml there-necked flask, add successively the bromo-1-propylmercaptan of 77g (0.5mol) 3-, 75g (0.5mol) chlorotriethyl silane, 100mlN, dinethylformamide.Then 37.4g (0.55mol) imidazoles is dissolved in to 40mlN, in dinethylformamide, by constant pressure funnel, splashes in there-necked flask, at 0 ℃, in 1 hour, dropwise, reaction system continues reaction 24 hours.Sodium hydrogen carbonate solution washing with 10% 3 times, with petroleum ether extraction, separates petroleum ether layer, on rotation musical instruments used in a Buddhist or Taoist mass, boils off solvent sherwood oil, through chromatographic column separation, obtains intermediate triethyl silicon sulfenyl propyl bromide, productive rate 91%.This reagent is kept in the brown bottle that fills hydrolith.
Embodiment 4: the preparation of tertiary butyl dimethyl-silicon sulfenyl-(2-methyl) propyl chloride
In 250ml there-necked flask, add successively 62g (0.5mol) 3-chloro-2-methyl-1-propylmercaptan, 75.3g (0.5mol) TERT-BUTYL DIMETHYL CHLORO SILANE, 100mlN, dinethylformamide.Then 37.4g (0.55mol) imidazoles is dissolved in to 40mlN, in dinethylformamide, by constant pressure funnel, splashes in there-necked flask, at 0 ℃, in 1 hour, dropwise, reaction system continues reaction 24 hours.Sodium hydrogen carbonate solution washing with 10% 3 times, with petroleum ether extraction, separates petroleum ether layer, on rotation musical instruments used in a Buddhist or Taoist mass, boils off solvent sherwood oil, through chromatographic column separation, obtains intermediate tertiary butyl dimethyl-silicon sulfenyl-(2-methyl) propyl chloride, productive rate 92%.This reagent is kept in the brown bottle that fills hydrolith.
Embodiment 5: the preparation of trimethyl silicane sulfenyl Butyryl Chloride
In 250ml there-necked flask, add successively the chloro-1-butyl sulfhydryl of 62g (0.5mol) 4-, 54g (0.5mol) trimethylchlorosilane, 100mlN, dinethylformamide.Then 37.4g (0.55mol) imidazoles is dissolved in to 40mlN, in dinethylformamide, by constant pressure funnel, splashes in there-necked flask, at 0 ℃, in 1 hour, dropwise, reaction system continues reaction 24 hours.Sodium hydrogen carbonate solution washing with 10% 3 times, with petroleum ether extraction, separates petroleum ether layer, on rotation musical instruments used in a Buddhist or Taoist mass, boils off solvent sherwood oil, through chromatographic column separation, obtains intermediate triethyl silicon sulfenyl propyl chloride, productive rate 95%.This reagent is kept in the brown bottle that fills hydrolith.
Embodiment 6: the preparation of tertiary butyl dimethyl-silicon sulfenyl propyl lithium
Under argon shield; to being equipped with in the 250ml there-necked flask of prolong, constant pressure funnel, magnetic agitation, add 16g (2.02mol) lithium and 100ml hexanaphthene; the tertiary butyl dimethyl-silicon sulfenyl propyl chloride that 67g (0.3mol) embodiment 1 is synthetic is miscible in 50ml hexanaphthene; by constant pressure funnel, in 1 hour, be added drop-wise in reaction flask; 60 ℃ of temperature of reaction; under magnetic agitation, react 4 hours, product filters and is stored in airtight container under argon shield.Adopting two its concentration of titration measuring of GILMAN is 0.86mol/L.
Embodiment 7: the preparation of tert-butyl diphenyl silicon sulfenyl propyl lithium
Under argon shield; to being equipped with in the 250ml there-necked flask of prolong, constant pressure funnel, magnetic agitation, add 16g (2.02mol) lithium and 100ml hexanaphthene; tertiary butyl dimethyl-silicon sulfenyl propyl bromide in 117.6g (0.3mol) embodiment 2 is miscible in 50ml hexanaphthene; by constant pressure funnel, in 1 hour, be added drop-wise in reaction flask; 50 ℃ of temperature of reaction; under magnetic agitation, react 5 hours, product filters and is stored in airtight container under argon shield.Adopting two its concentration of titration measuring of GILMAN is 0.82mol/L.
Embodiment 8: the preparation of triethyl silicon sulfenyl propyl lithium
Under argon shield; to being equipped with in the 250ml there-necked flask of prolong, constant pressure funnel, magnetic agitation, add 16g (2.02mol) lithium and 100ml hexanaphthene; 76.2g (0.3mol) triethyl silicon sulfenyl propyl bromide is miscible in 50ml hexanaphthene; by constant pressure funnel, add in reaction flask; 45 ℃ of temperature of reaction; under magnetic agitation, react 6 hours, product filters and is stored in airtight container under argon shield.Adopting two its concentration of titration measuring of GILMAN is 0.78mol/L.
Embodiment 9: the preparation of tertiary butyl dimethyl-silicon sulfenyl-(2-methyl) propyl lithium
Under argon shield; to being equipped with in the 250ml there-necked flask of prolong, constant pressure funnel, magnetic agitation, add 16g (2.02mol) lithium and 100ml hexanaphthene; 71.4g (0.3mol) tertiary butyl dimethyl-silicon sulfenyl-(2-methyl) propyl chloride is miscible in 50ml hexanaphthene; by constant pressure funnel, add in reaction flask; 60 ℃ of temperature of reaction; under magnetic agitation, react 4 hours, product filters and is stored in airtight container under argon shield.Adopting two its concentration of titration measuring of GILMAN is 0.88mol/L.
Embodiment 10: synthetic (the Isosorbide-5-Nitrae structural content 90%) of two sulfydryl polyhutadiene
By removing clean 100ml reactor, vacuumize backlash argon gas, repeat this operation three times, then in argon gas atmosphere environment, at-10～-8 ℃, add successively the tertiary butyl dimethyl Si base propyl lithium 2.9ml in hexanaphthene 50ml, divinyl 10g, embodiment 6,50 ± 2 ℃ are reacted 2～2.5 hours.To injection ring oxidative ethane in reactor, react 1～1.5 hour again, finally inject methyl alcohol and stop.Polymkeric substance condenses with ethanol, obtains white thick material, is dissolved in the tetrahydrofuran (THF) of hcl acidifying, reacts 1.0～1.5 hours, with being dried and within 10-12 hour, just obtaining both-end sulfydryl polyhutadiene at 70-80 ℃ after ethanol cohesion, washing under room temperature.With VPO, recording number-average molecular weight is 4120, with GPC determining molecular weight, is distributed as 1.06, with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, is 90%, and functionality is about 2.0.
Embodiment 11: synthetic (the Isosorbide-5-Nitrae structural content 50%) of two sulfydryl polyhutadiene
By removing clean reactor, vacuumize backlash argon gas, repeat this operation three times, then in argon gas atmosphere environment, at-10～-8 ℃, add successively the tertiary butyl dimethyl Si base propyl lithium 2.9ml in hexanaphthene 25ml, tetrahydrofuran (THF) 25ml, divinyl 10g, embodiment 6,50 ± 2 ℃ are reacted 2～2.5 hours.To injection ring oxidative ethane in reactor, react 1～1.5 hour again, finally inject methyl alcohol and stop.Polymkeric substance condenses with ethanol, obtains white thick material, is dissolved in the tetrahydrofuran (THF) of hcl acidifying, reacts 1.0～1.5 hours, with being dried and within 10-12 hour, just obtaining both-end sulfydryl polyhutadiene at 70-80 ℃ after ethanol cohesion, washing under room temperature.With VPO, recording number-average molecular weight is 4320, with GPC determining molecular weight, is distributed as 1.12, with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, is 50%, and functionality is about 2.0.
Embodiment 12: synthetic (the Isosorbide-5-Nitrae structural content 10%) of two sulfydryl polyhutadiene
By removing clean reactor, vacuumize backlash argon gas, repeat this operation three times, then in argon gas atmosphere environment, at-10～-8 ℃, add successively the tertiary butyl dimethyl Si base propyl lithium 2.9ml in tetrahydrofuran (THF) 50ml, divinyl 10g, embodiment 6,50 ± 2 ℃ are reacted 2～2.5 hours.To the trimethyl silicane sulfenyl Butyryl Chloride 1.0g that injects embodiment 5 in reactor, react 2 hours again.Polymkeric substance condenses with ethanol, obtains white thick material, is dissolved in the tetrahydrofuran (THF) of hcl acidifying, reacts 2 hours, with being dried and within 10-12 hour, just obtaining both-end sulfydryl polyhutadiene at 70-80 ℃ after ethanol cohesion, washing under room temperature.With VPO, recording number-average molecular weight is 4115, with GPC determining molecular weight, is distributed as 1.15, with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, is 10%, and functionality is about 2.0.
Embodiment 13: two sulfydryl polyisoprene synthetic
By removing clean 100ml reactor, vacuumize backlash argon gas, repeat this operation three times, then in argon gas atmosphere environment, at-10～-8 ℃, add successively the tertiary butyl dimethyl-silicon sulfenyl propyl lithium 2.9ml in hexanaphthene 50ml, isoprene 10g, embodiment 6,50 ± 2 ℃ are reacted 2～2.5 hours.To the trimethyl silicane sulfenyl Butyryl Chloride 1.0g that injects embodiment 5 in reactor, react 2 hours again.Polymkeric substance condenses with ethanol, obtains white thick material, is dissolved in the tetrahydrofuran (THF) of hcl acidifying, reacts 2 hours, with being dried and within 10-12 hour, just obtaining both-end sulfydryl polyisoprene at 70-80 ℃ after ethanol cohesion, washing under room temperature.With VPO, recording number-average molecular weight is 4083, with GPC determining molecular weight, is distributed as 1.15, with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, is 90%, and functionality is about 2.0.
Embodiment 14: two sulfydryl polyisoprene-divinyl diblock copolymers synthetic
By removing clean 100ml reactor, vacuumize backlash argon gas, repeat this operation three times, then in argon gas atmosphere environment, at-10～-8 ℃, add successively the tertiary butyl dimethyl-silicon sulfenyl propyl lithium 2.9ml in hexanaphthene 50ml, isoprene 5g, embodiment 6,50 ± 2 ℃ are reacted 1～1.5 hour, then add divinyl 5g, react 1～1.5 hour.To the triethyl silicon sulfenyl propyl bromide 1.27g that injects embodiment 4 in reactor, react 2 hours again.Polymkeric substance condenses with ethanol, obtain white thick material, be dissolved in the tetrahydrofuran (THF) of hcl acidifying, under room temperature, reacted 2 hours, with being dried and within 10-12 hour, just obtaining both-end sulfydryl polyisoprene-divinyl diblock copolymer at 70-80 ℃ after ethanol cohesion, washing.With VPO, recording number-average molecular weight is 3956, with GPC determining molecular weight, is distributed as 1.18, with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, is 90%, and functionality is about 2.0.
Synthesizing of 15 pairs of sulfydryl Styrene Butadiene Copolymer of embodiment
By removing clean 100ml reactor, vacuumize backlash argon gas, repeat this operation three times, then in argon gas atmosphere environment, at-10～-8 ℃, add successively the tertiary butyl dimethyl-silicon sulfenyl propyl lithium 2.9ml in hexanaphthene 50ml, divinyl 5g, embodiment 6,50 ± 2 ℃ are reacted 1～1.5 hour, then adding 5g vinylbenzene, 50 ± 2 ℃ are reacted 1～1.5 hour.To the trimethyl silicane sulfenyl Butyryl Chloride 1.0g that injects embodiment 5 in reactor, react 2 hours again.Polymkeric substance condenses with ethanol, obtains white thick material, is dissolved in the tetrahydrofuran (THF) of hcl acidifying, reacts 2 hours, with being dried and within 10-12 hour, just obtaining both-end sulfydryl polyisoprene at 70-80 ℃ after ethanol cohesion, washing under room temperature.With VPO, recording number-average molecular weight is 4083, with GPC determining molecular weight, is distributed as 1.15, and functionality is about 2.0.
Synthesizing of embodiment 16 3 arm star end sulfydryl polyhutadiene
By removing clean 100ml reactor, vacuumize backlash argon gas, repeat this operation three times, then in argon gas atmosphere environment, at-10～-8 ℃, add successively the tertiary butyl dimethyl-silicon sulfenyl propyl lithium 8.7ml in hexanaphthene 50ml, polyhutadiene 10g, embodiment 6,50 ± 2 ℃ are reacted 2～2.5 hours, in reactor, inject METHYL TRICHLORO SILANE 1.11g again, react 2 hours.Polymkeric substance condenses with ethanol, obtain white thick material, be dissolved in the tetrahydrofuran (THF) of hcl acidifying, under room temperature, reacted 2 hours, with being dried and within 10-12 hour, just obtaining both-end sulfydryl polyisoprene-divinyl diblock copolymer at 70-80 ℃ after ethanol cohesion, washing.With VPO, recording number-average molecular weight is 4101, with GPC determining molecular weight, is distributed as 1.09, with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, is 90%, and number-average is about 2.9.
Claims (1)
1. a preparation method for both-end sulfydryl polymkeric substance, is characterized in that:
(1) initiator intermediate is synthetic:
Sulfhydryl protected reagent and halo mercaptan are dissolved in and are placed in reaction flask in the ratio of molar weight 1:1, volume is in the polar solvent of 3 times, halo mercaptan, the catalyzer that is in excess in sulfhydryl protected reagent or halo mercaptan molar weight 10% is dissolved in the same polar solvent of 2 times of its quality, and splash in reaction flask by constant pressure funnel, temperature of reaction is-5 ℃～5 ℃, 24 hours reaction times, resultant washs three times with 5% sodium hydrogen carbonate solution afterwards, with weak polar solvent, extract, get supernatant liquid and on Rotary Evaporators, boil off solvent, with column chromatography separation, obtain initiator intermediate again,
Said polar solvent has N, dinethylformamide or dimethyl sulfoxide (DMSO);
Sulfhydryl protected reagent used is TERT-BUTYL DIMETHYL CHLORO SILANE, tert-butyl diphenyl chlorosilane, trimethylchlorosilane, chlorotriethyl silane or tripropyl chlorine silicon;
Said halo mercaptan is selected from the chloro-1-sulfur alcohol of 2-, the chloro-1-propylmercaptan of 3-, the bromo-1-sulfur alcohol of 2-, the bromo-1-propylmercaptan of 3-, the chloro-1-butyl sulfhydryl of 4-or 3-chloro-2-methyl-1-propylmercaptan;
Said catalyzer is imidazoles, pyrimidine or pyridine;
Said weak polar solvent sherwood oil or normal hexane;
(2) preparation of initiator
Initiator intermediate is reacted and is prepared from by molar weight 1:6.7 with metallic lithium in the non-polar solvent of 3 times of initiator intermediate volumes, and initiator intermediate adds in reaction system by constant pressure funnel, and temperature of reaction is 30-70 ℃;
Non-polar solvent is hexanaphthene, normal hexane or benzene;
(3) reactive polymer is synthetic
Successively solvent, initiator, monomer and structure regulator are added in reactor, wherein solvent volume amount is 4 times of monomer volume, and initiator and structure regulator consumption are respectively: in monomer mass 10g, initiator amount is 0.001～0.01moL; Structure regulator consumption is 0～4 times of monomer volume; After treating monomer reaction, just obtain reactive polymer, temperature of reaction is 0-60 ℃;
Said monomer is divinyl, vinylbenzene or isoprene;
Said solvent is hexanaphthene, normal hexane or benzene;
Said structure regulator is tetrahydrofuran (THF), Tetramethyl Ethylene Diamine or diglyme;
(4) end-blocking of reactive polymer and termination
Equivalent is added after reacting half an hour in reactive polymer and adds methyl alcohol to stop in the capping reagent of initiator molar weight; Or add functionalized terminator reaction 1 hour; Or add coupling agent reaction 1.5 hours; Complete the termination of reactive polymer;
Said capping reagent is thiirane or epithio propane, and functionalized terminator is synthetic initiator intermediate;
Said coupling agent is METHYL TRICHLORO SILANE or tetrachloro silicane;
(5) blocking group removes
By stopping complete polymkeric substance, be dissolved in solvent, 10% the mineral acid acidifying 2 hours with being in excess in initiator amount of substance, has completed removing of blocking group, just obtains pure both-end sulfydryl polymkeric substance by polymers soln is dry afterwards.
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| US6579949B1 (en) * | 2001-10-30 | 2003-06-17 | Bridgestone Corporation | Preparation of low hysteresis rubber by reacting a lithium polymer with a sulfur containing reagent |
| CN101104654A (en) * | 2007-07-05 | 2008-01-16 | 复旦大学 | A kind of polymer with multiple functional groups in terminal group and preparation method thereof |
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| EP1721912A4 (en) * | 2004-03-01 | 2008-07-16 | Kuraray Co | PROCESS FOR PRODUCING A POLYMER HAVING AN END WITH A FUNCTIONAL GROUP |
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| US6579949B1 (en) * | 2001-10-30 | 2003-06-17 | Bridgestone Corporation | Preparation of low hysteresis rubber by reacting a lithium polymer with a sulfur containing reagent |
| CN101104654A (en) * | 2007-07-05 | 2008-01-16 | 复旦大学 | A kind of polymer with multiple functional groups in terminal group and preparation method thereof |
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