CN102924638A - Preparation method of double-end sulfhydryl polymer - Google Patents
Preparation method of double-end sulfhydryl polymer Download PDFInfo
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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 the field of end functionalized polymer preparation, 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
The 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, because the liquid performance of its special active end group and normal temperature makes it have the special purpose that solid rubber can't be compared.For example both-end sulfydryl polyhutadiene is because its special sulfydryl makes it faster than both-end hydroxyl polyhutadiene curing speed at normal temperatures, so successfully be used 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.
The end group conversion method namely 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 several methods that transform by end group prepare the method for holding the sulfydryl polymkeric substance.Although the both-end sulfydryl polymkeric substance step of end group conversion method preparation is simple, owing to have the not high problem of transformation efficiency in the end group conversion process, so remain the material of other functional group in the end sulfydryl polymkeric substance that makes.On the other hand, because the end functionalized base polymer of liquid is in re-starting the 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, such as USP3,240,844 and USP3, the preparation of the end sulfydryl polymkeric substance of mentioning in 755,269, the both-end sulfydryl polyhutadiene of the method preparation or both-end sulfydryl isoprene fluid rubber are because in the microtexture 1, content is higher in 2 structures, so the apparent viscosity of polymkeric substance is larger.And the pseudo-gels phenomenon in the end-blocking process, occurs easily, so affected the average functionality of polymkeric substance.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing both-end sulfydryl polymkeric substance, the method adopts the anionic initiator trigger monomer polymerization with protected silane sulfydryl, preparation both-end sulfydryl polymkeric substance.
The both-end sulfydryl polymkeric substance that the present invention relates to, its general structure is as follows:
R wherein
1, R
2For carbon atom is straight-chain paraffin or the branched paraffin of 1-10, 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. the 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 is dissolved in 1: 1 ratio of molar weight places reaction flask, volume is in the polar solvent of 3 times in 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 the reaction flask by constant pressure funnel, temperature of reaction is-5 ℃～5 ℃, 24 hours reaction times, resultant is with 5% sodium hydrogen carbonate solution washing three times afterwards, extract with weak polar solvent, get supernatant liquid and boil off solvent at Rotary Evaporators, separate again obtaining the initiator intermediate with column chromatography;
Said polar solvent has N, dinethylformamide or dimethyl sulfoxide (DMSO);
Used sulfhydryl protected reagent is TERT-BUTYL DIMETHYL CHLORO SILANE, tert-butyl diphenyl chlorosilane, trimethylchlorosilane, chlorotriethyl silane or tripropyl chlorine silicon;
Said halo mercaptan is selected from 2-chloro-1-sulfur alcohol, 3-chloro-1-propylmercaptan, 2-bromo-1-sulfur alcohol, 3-bromo-1-propylmercaptan, 4-chloro-1-butyl sulfhydryl 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 and metallic lithium in the non-polar solvent of initiator intermediate volume 3 times reacted by molar weight at 1: 6.7 be prepared from, the initiator intermediate adds in the 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 the reactor, wherein the 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; The structure regulator consumption is 0～4 times of monomer volume.After monomer reaction is complete, 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 reaction in the capping reagent adding reactive polymer of initiator molar weight is added methyl alcohol after half an hour to be stopped; Perhaps add functionalized terminator reaction 1 hour; Perhaps add coupling agent reaction 1.5 hours; Finish 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
Be dissolved in the solvent stopping complete polymkeric substance, with 10% the mineral acid acidifying that is in excess in the initiator amount of substance 2 hours, finished removing of blocking group, afterwards the polymers soln drying is just obtained pure both-end sulfydryl polymkeric substance.
Said mineral acid comprises dilute hydrochloric acid, rare nitric acid or dilute sulphuric acid, preferentially selects dilute hydrochloric acid.
Compare the method for preparing end sulfydryl polymkeric substance of present report, this law has following advantage:
1. adopted the initiator that contains the 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 add structure regulator in non-polar solvent, 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 be regulated 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 (less than 1.20), the molecular size range in the preparation process is regulated easily.
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 gelatin phenomenon can not appear all, resulting polymkeric substance functionality is near 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 the 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 the 250ml there-necked flask, add successively 55.0g (0.5mol) 3-chloro-1-propylmercaptan, 75.3g (0.5mol) TERT-BUTYL DIMETHYL CHLORO SILANE, 100mlN, dinethylformamide.Then 37.4g (0.55mol) imidazoles is dissolved in 40mlN, in the dinethylformamide, splashes in the there-necked flask by constant pressure funnel, dropwise in lower 1 hour at 0 ℃, reaction system continues reaction 24 hours.Then with 10% sodium hydrogen carbonate solution washing 3 times, use petroleum ether extraction, tell petroleum ether layer, boil off the solvent sherwood oil at rotatory evaporator, obtaining intermediate tertiary butyl dimethyl-silicon sulfenyl propyl chloride, productive rate 95% through the chromatographic column separation.This reagent is kept in the brown bottle that fills hydrolith.
Embodiment 2: the preparation of tert-butyl diphenyl silicon sulfenyl propyl bromide
In the 250ml there-necked flask, add successively 77g (0.5mol) 3-bromo-1-propylmercaptan, 137.5g (0.5mol) tert-butyl diphenyl chlorosilane, 100mlN, dinethylformamide.Then 37.4g (0.55mol) imidazoles is dissolved in 40mlN, in the dinethylformamide, splashes in the there-necked flask by constant pressure funnel, dropwise in lower 1 hour at 0 ℃, reaction system continues reaction 24 hours.Petroleum ether extraction is used in sodium hydrogen carbonate solution washing with 10% 3 times, tells petroleum ether layer, boils off the solvent sherwood oil at the rotation musical instruments used in a Buddhist or Taoist mass, separates obtaining intermediate tert-butyl diphenyl silicon sulfenyl propyl bromide, productive rate 90% through chromatographic column.This reagent is kept in the brown bottle that fills hydrolith.
Embodiment 3: the preparation of triethyl silicon sulfenyl propyl bromide
In the 250ml there-necked flask, add successively 77g (0.5mol) 3-bromo-1-propylmercaptan, 75g (0.5mol) chlorotriethyl silane, 100mlN, dinethylformamide.Then 37.4g (0.55mol) imidazoles is dissolved in 40mlN, in the dinethylformamide, splashes in the there-necked flask by constant pressure funnel, dropwise in lower 1 hour at 0 ℃, reaction system continues reaction 24 hours.Petroleum ether extraction is used in sodium hydrogen carbonate solution washing with 10% 3 times, tells petroleum ether layer, boils off the solvent sherwood oil at the rotation musical instruments used in a Buddhist or Taoist mass, separates obtaining intermediate triethyl silicon sulfenyl propyl bromide, productive rate 91% through chromatographic column.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 the 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 40mlN, in the dinethylformamide, splashes in the there-necked flask by constant pressure funnel, dropwise in lower 1 hour at 0 ℃, reaction system continues reaction 24 hours.Petroleum ether extraction is used in sodium hydrogen carbonate solution washing with 10% 3 times, tells petroleum ether layer, boils off the solvent sherwood oil at the rotation musical instruments used in a Buddhist or Taoist mass, separates obtaining intermediate tertiary butyl dimethyl-silicon sulfenyl-(2-methyl) propyl chloride, productive rate 92% through chromatographic column.This reagent is kept in the brown bottle that fills hydrolith.
Embodiment 5: the preparation of trimethyl silicane sulfenyl Butyryl Chloride
In the 250ml there-necked flask, add successively 62g (0.5mol) 4-chloro-1-butyl sulfhydryl, 54g (0.5mol) trimethylchlorosilane, 100mlN, dinethylformamide.Then 37.4g (0.55mol) imidazoles is dissolved in 40mlN, in the dinethylformamide, splashes in the there-necked flask by constant pressure funnel, dropwise in lower 1 hour at 0 ℃, reaction system continues reaction 24 hours.Petroleum ether extraction is used in sodium hydrogen carbonate solution washing with 10% 3 times, tells petroleum ether layer, boils off the solvent sherwood oil at the rotation musical instruments used in a Buddhist or Taoist mass, separates obtaining intermediate triethyl silicon sulfenyl propyl chloride, productive rate 95% through chromatographic column.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; in the 250ml there-necked flask that prolong, constant pressure funnel, magnetic agitation are housed, add 16g (2.02mol) lithium and 100ml hexanaphthene; 67g (0.3mol) embodiment 1 synthetic tertiary butyl dimethyl-silicon sulfenyl propyl chloride is miscible in the 50ml hexanaphthene; be added drop-wise in the reaction flask in 1 hour by constant pressure funnel; 60 ℃ of temperature of reaction; reaction is 4 hours under magnetic agitation, and product filters under argon shield and is stored in the airtight container.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; in the 250ml there-necked flask that prolong, constant pressure funnel, magnetic agitation are housed, add 16g (2.02mol) lithium and 100ml hexanaphthene; tertiary butyl dimethyl-silicon sulfenyl propyl bromide among 117.6g (0.3mol) embodiment 2 is miscible in the 50ml hexanaphthene; be added drop-wise in the reaction flask in 1 hour by constant pressure funnel; 50 ℃ of temperature of reaction; reaction is 5 hours under magnetic agitation, and product filters under argon shield and is stored in the airtight container.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; in the 250ml there-necked flask that prolong, constant pressure funnel, magnetic agitation are housed, add 16g (2.02mol) lithium and 100ml hexanaphthene; 76.2g (0.3mol) triethyl silicon sulfenyl propyl bromide is miscible in the 50ml hexanaphthene; add in the reaction flask by constant pressure funnel; 45 ℃ of temperature of reaction; reaction is 6 hours under magnetic agitation, and product filters under argon shield and is stored in the airtight container.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; in the 250ml there-necked flask that prolong, constant pressure funnel, magnetic agitation are housed, add 16g (2.02mol) lithium and 100ml hexanaphthene; 71.4g (0.3mol) tertiary butyl dimethyl-silicon sulfenyl-(2-methyl) propyl chloride is miscible in the 50ml hexanaphthene; add in the reaction flask by constant pressure funnel; 60 ℃ of temperature of reaction; reaction is 4 hours under magnetic agitation, and product filters under argon shield and is stored in the airtight container.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
Vacuumize the backlash argon gas with removing clean 100ml reactor, repeat this operation three times, then add successively the tertiary butyl dimethyl Si base propyl lithium 2.9ml among hexanaphthene 50ml, divinyl 10g, the embodiment 6 in the argon gas atmosphere environment under-10～-8 ℃, 50 ± 2 ℃ were reacted 2～2.5 hours.Injection ring oxidative ethane in the reactor reacted 1～1.5 hour again, injected at last methyl alcohol and stopped.Polymkeric substance condenses with ethanol, obtains white thick material, and it is dissolved in the tetrahydrofuran (THF) of hcl acidifying, reacts under the room temperature 1.0～1.5 hours, just obtains down both-end sulfydryl polyhutadiene in dry 10-12 hour at 70-80 ℃ afterwards with ethanol cohesion, washing.Recording number-average molecular weight with VPO is 4120, is distributed as 1.06 with the GPC determining molecular weight, is 90% with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, and functionality is about 2.0.
Embodiment 11: synthetic (the Isosorbide-5-Nitrae structural content 50%) of two sulfydryl polyhutadiene
Vacuumize the backlash argon gas with removing clean reactor, repeat this operation three times, then add successively the tertiary butyl dimethyl Si base propyl lithium 2.9ml among hexanaphthene 25ml, tetrahydrofuran (THF) 25ml, divinyl 10g, the embodiment 6 in the argon gas atmosphere environment under-10～-8 ℃, 50 ± 2 ℃ were reacted 2～2.5 hours.Injection ring oxidative ethane in the reactor reacted 1～1.5 hour again, injected at last methyl alcohol and stopped.Polymkeric substance condenses with ethanol, obtains white thick material, and it is dissolved in the tetrahydrofuran (THF) of hcl acidifying, reacts under the room temperature 1.0～1.5 hours, just obtains down both-end sulfydryl polyhutadiene in dry 10-12 hour at 70-80 ℃ afterwards with ethanol cohesion, washing.Recording number-average molecular weight with VPO is 4320, is distributed as 1.12 with the GPC determining molecular weight, is 50% with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, and functionality is about 2.0.
Embodiment 12: synthetic (the Isosorbide-5-Nitrae structural content 10%) of two sulfydryl polyhutadiene
Vacuumize the backlash argon gas with removing clean reactor, repeat this operation three times, then add successively the tertiary butyl dimethyl Si base propyl lithium 2.9ml among tetrahydrofuran (THF) 50ml, divinyl 10g, the embodiment 6 in the argon gas atmosphere environment under-10～-8 ℃, 50 ± 2 ℃ were reacted 2～2.5 hours.Inject again the trimethyl silicane sulfenyl Butyryl Chloride 1.0g of embodiment 5 in the reactor, reacted 2 hours.Polymkeric substance condenses with ethanol, obtains white thick material, and it is dissolved in the tetrahydrofuran (THF) of hcl acidifying, and reaction is 2 hours under the room temperature, with just obtaining both-end sulfydryl polyhutadiene in lower dry 10-12 hour at 70-80 ℃ after ethanol cohesion, the washing.Recording number-average molecular weight with VPO is 4115, is distributed as 1.15 with the GPC determining molecular weight, is 10% with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, and functionality is about 2.0.
Embodiment 13: two sulfydryl polyisoprene synthetic
Vacuumize the backlash argon gas with removing clean 100ml reactor, repeat this operation three times, then add successively the tertiary butyl dimethyl-silicon sulfenyl propyl lithium 2.9ml among hexanaphthene 50ml, isoprene 10g, the embodiment 6 in the argon gas atmosphere environment under-10～-8 ℃, 50 ± 2 ℃ were reacted 2～2.5 hours.Inject again the trimethyl silicane sulfenyl Butyryl Chloride 1.0g of embodiment 5 in the reactor, reacted 2 hours.Polymkeric substance condenses with ethanol, obtains white thick material, and it is dissolved in the tetrahydrofuran (THF) of hcl acidifying, and reaction is 2 hours under the room temperature, with just obtaining both-end sulfydryl polyisoprene in lower dry 10-12 hour at 70-80 ℃ after ethanol cohesion, the washing.Recording number-average molecular weight with VPO is 4083, is distributed as 1.15 with the GPC determining molecular weight, is 90% with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, and functionality is about 2.0.
Embodiment 14: two sulfydryl polyisoprene-divinyl diblock copolymer synthetic
Vacuumize the backlash argon gas with removing clean 100ml reactor, repeat this operation three times, then in the argon gas atmosphere environment, under-10～-8 ℃, add successively the tertiary butyl dimethyl-silicon sulfenyl propyl lithium 2.9ml among hexanaphthene 50ml, isoprene 5g, the embodiment 6,50 ± 2 ℃ were reacted 1～1.5 hour, then add divinyl 5g, reacted 1～1.5 hour.Inject again the triethyl silicon sulfenyl propyl bromide 1.27g of embodiment 4 in the reactor, reacted 2 hours.Polymkeric substance condenses with ethanol, obtain white thick material, it is dissolved in the tetrahydrofuran (THF) of hcl acidifying, and reaction is 2 hours under the room temperature, with just obtaining both-end sulfydryl polyisoprene-divinyl diblock copolymer in lower dry 10-12 hour at 70-80 ℃ after ethanol cohesion, the washing.Recording number-average molecular weight with VPO is 3956, is distributed as 1.18 with the GPC determining molecular weight, is 90% with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, and functionality is about 2.0.
Synthesizing of 15 pairs of sulfydryl Styrene Butadiene Copolymer of embodiment
Vacuumize the backlash argon gas with removing clean 100ml reactor, repeat this operation three times, then in the argon gas atmosphere environment, under-10～-8 ℃, add successively the tertiary butyl dimethyl-silicon sulfenyl propyl lithium 2.9ml among hexanaphthene 50ml, divinyl 5g, the embodiment 6,50 ± 2 ℃ were reacted 1～1.5 hour, then adding 5g vinylbenzene, 50 ± 2 ℃ were reacted 1～1.5 hour.Inject again the trimethyl silicane sulfenyl Butyryl Chloride 1.0g of embodiment 5 in the reactor, reacted 2 hours.Polymkeric substance condenses with ethanol, obtains white thick material, and it is dissolved in the tetrahydrofuran (THF) of hcl acidifying, and reaction is 2 hours under the room temperature, with just obtaining both-end sulfydryl polyisoprene in lower dry 10-12 hour at 70-80 ℃ after ethanol cohesion, the washing.Recording number-average molecular weight with VPO is 4083, is distributed as 1.15 with the GPC determining molecular weight, and functionality is about 2.0.
Synthesizing of embodiment 16 3 arm star end sulfydryl polyhutadiene
Vacuumize the backlash argon gas with removing clean 100ml reactor, repeat this operation three times, then in the argon gas atmosphere environment, under-10～-8 ℃, add successively the tertiary butyl dimethyl-silicon sulfenyl propyl lithium 8.7ml among hexanaphthene 50ml, polyhutadiene 10g, the embodiment 6,50 ± 2 ℃ were reacted 2～2.5 hours, in reactor, inject METHYL TRICHLORO SILANE 1.11g again, reacted 2 hours.Polymkeric substance condenses with ethanol, obtain white thick material, it is dissolved in the tetrahydrofuran (THF) of hcl acidifying, and reaction is 2 hours under the room temperature, with just obtaining both-end sulfydryl polyisoprene-divinyl diblock copolymer in lower dry 10-12 hour at 70-80 ℃ after ethanol cohesion, the washing.Recording number-average molecular weight with VPO is 4101, is distributed as 1.09 with the GPC determining molecular weight, is 90% with nucleus magnetic resonance somatotype Isosorbide-5-Nitrae structural content, and the number-average is about 2.9.
Claims (1)
1. the preparation method of a both-end sulfydryl polymkeric substance is characterized in that:
(1) the initiator intermediate is synthetic:
Sulfhydryl protected reagent and halogen band mercaptan is dissolved in 1: 1 ratio of molar weight places reaction flask, volume is in the polar solvent of 3 times in 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 the reaction flask by constant pressure funnel, temperature of reaction is-5 ℃～5 ℃, 24 hours reaction times, resultant is with 5% sodium hydrogen carbonate solution washing three times afterwards, extract with weak polar solvent, get supernatant liquid and boil off solvent at Rotary Evaporators, separate again obtaining the initiator intermediate with column chromatography;
Said polar solvent has N, dinethylformamide or dimethyl sulfoxide (DMSO);
Used sulfhydryl protected reagent is TERT-BUTYL DIMETHYL CHLORO SILANE, tert-butyl diphenyl chlorosilane, trimethylchlorosilane, chlorotriethyl silane or tripropyl chlorine silicon;
Said halo mercaptan is selected from 2-chloro-1-sulfur alcohol, 3-chloro-1-propylmercaptan, 2-bromo-1-sulfur alcohol, 3-bromo-1-propylmercaptan, 4-chloro-1-butyl sulfhydryl 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 and metallic lithium in the non-polar solvent of initiator intermediate volume 3 times reacted by molar weight at 1: 6.7 be prepared from, the initiator intermediate adds in the 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 the reactor, wherein the 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; The structure regulator consumption is 0～4 times of monomer volume; After monomer reaction is complete, 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 reaction in the capping reagent adding reactive polymer of initiator molar weight is added methyl alcohol after half an hour to be stopped; Perhaps add functionalized terminator reaction 1 hour; Perhaps add coupling agent reaction 1.5 hours; Finish 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
Be dissolved in the solvent stopping complete polymkeric substance, with 10% the mineral acid acidifying that is in excess in the initiator amount of substance 2 hours, finished removing of blocking group, afterwards the polymers soln drying is just obtained pure both-end sulfydryl polymkeric substance.
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| CN106565904A (en) * | 2015-10-10 | 2017-04-19 | 中国石油天然气股份有限公司 | Bifunctionalized styrene-butadiene polymer, preparation method thereof, rubber composition and vulcanized rubber |
| CN113403002A (en) * | 2021-07-12 | 2021-09-17 | 江苏国立化工科技有限公司 | Method and device for producing rubber adhesive |
| CN113492018A (en) * | 2020-04-01 | 2021-10-12 | 丹东明珠特种树脂有限公司 | Resin catalyst for bisphenol A synthesis, preparation method thereof and application of bisphenol A catalytic synthesis thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106565904A (en) * | 2015-10-10 | 2017-04-19 | 中国石油天然气股份有限公司 | Bifunctionalized styrene-butadiene polymer, preparation method thereof, rubber composition and vulcanized rubber |
| CN106565904B (en) * | 2015-10-10 | 2019-03-12 | 中国石油天然气股份有限公司 | Bifunctionalized styrene-butadiene polymer, preparation method thereof, rubber composition and vulcanized rubber |
| CN113492018A (en) * | 2020-04-01 | 2021-10-12 | 丹东明珠特种树脂有限公司 | Resin catalyst for bisphenol A synthesis, preparation method thereof and application of bisphenol A catalytic synthesis thereof |
| CN113492018B (en) * | 2020-04-01 | 2024-01-09 | 丹东明珠特种树脂有限公司 | Resin catalyst for bisphenol A synthesis and application of bisphenol A in catalytic synthesis |
| CN113403002A (en) * | 2021-07-12 | 2021-09-17 | 江苏国立化工科技有限公司 | Method and device for producing rubber adhesive |
| CN113403002B (en) * | 2021-07-12 | 2023-02-10 | 江苏国立化工科技有限公司 | Method and device for producing rubber adhesive |
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| CN102924638B (en) | 2014-04-02 |
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