CN102453047B - Alkylsiloxy-1-halogenated aliphatic alkane, and preparation and application thereof - Google Patents
Alkylsiloxy-1-halogenated aliphatic alkane, and preparation and application thereof Download PDFInfo
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- CN102453047B CN102453047B CN201010522222.1A CN201010522222A CN102453047B CN 102453047 B CN102453047 B CN 102453047B CN 201010522222 A CN201010522222 A CN 201010522222A CN 102453047 B CN102453047 B CN 102453047B
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Abstract
The invention relates to an alkylsiloxy-1-halogenated aliphatic alkane, and preparation and application thereof. The preparation method comprises the following steps: dissolving halogenated silane and halogenated alcohol in a mol ratio of (1-1.3):1 in a polar solvent, dropwisely adding imidazole or pyrimidine (accounting for 80-130 mol% of halogenated silane) within 30 minutes in an argon atmosphere while controlling the temperature at -5-5 DEG C, heating to 20-50 DEG C, and reacting for 4-8 hours; and adding a non-polar solvent which is 2-5 times of the polar solvent by volume, washing with a sodium bicarbonate solution, stratifying a non-polar solvent layer, and evaporating with a rotary evaporator to remove the solvent, thereby obtaining the alkylsiloxy-1-halogenated aliphatic alkane solution. The alpha-terminated polymer active chain terminator used in the process of preparing the alpha,omega-terminated functional polymer has mild active chain conditions, and can not form dimers; and the protecting group silane group can be easily removed in the hydrochloric acid acidified polar solvent.
Description
Technical field
The present invention relates to a kind of Alkylsiloxy-1-halogenated aliphatic alkane and preparation thereof and application.
Background technology
α, during the negatively charged ion of omega end functionalized polymeric synthesizes, " block " of polymer active chain or termination tech are one of important steps in its preparation process.According to spike in polymer active chain number, " block " or stop being divided into single " block " or termination, two " blocks " or stop and many " blocks " or termination.Single " block " or termination procedure are mainly applicable to protect the functionalized of the active straight chain of functionalized polymeric list; two " blocks " or termination procedure are mainly applicable to the functionalized of polymkeric substance double activated straight chain, and many " blocks " or termination procedure are mainly used in the functionalized of three or three above polymer active side chains.
When living anion polymerization is prepared end group polymer, the two lithiums of the alkyl of usining are as initiator, and epoxies alkane, aldehydes, carbonic acid gas etc. are as " block " reagent, this method
o
-li
+between or Li
+o
- 
o
-li
*there is pseudo-gels phenomenon because there is serious self-association in inside, affects polymkeric substance average functionality.The blocking group of the company such as Phillips Petroleum Company and the GeneralTire and Rubber Company employing afterwards lithium alkylide is initiator; ethylene oxide/propylene oxide, formaldehyde/acetaldehyde, carbonic acid gas etc. are " block " reagent; although this method can be avoided pseudo-gels phenomenon; but because of " block " reagent boiling point too low; be difficult for refining, the defects such as " block " complex process cause average functionality to be no more than 1.9.
In order to find better more easy polymer active chain " block " or terminating method, AHirao, H Nagahama etc. are with BrCH
2cH
2cH
2c (OCH
3)
3as terminator, obtained poly-ω-COOH polymkeric substance, but the people such as Mechin found that this method was because Br-Li permutoid reaction forms a large amount of dimers afterwards, made its molecular weight double.
Summary of the invention
The object of this invention is to provide a kind of Alkylsiloxy-1-halogenated aliphatic alkane and preparation thereof and application; For α, synthesizing of omega end alkyl siloxy polymkeric substance, obtains α, omega end based polyalcohol through removing blocking group.
(1) Alkylsiloxy-1-halogenated aliphatic alkane
Alkylsiloxy-1-halogenated aliphatic alkane of the present invention, its molecular structural formula is as follows:
R
1, R
2, R
3for: CH
3-[CH
2]-
mor
or
by one or more; The integer that wherein m is 0～4;
R
4for
Wherein, R
5for
n is 1～5 integer,
R
6for H or
m is 0～6 integer;
X is Cl or Br.
(2) preparation of Alkylsiloxy-1-halogenated aliphatic alkane
The preparation method of Alkylsiloxy-1-halogenated aliphatic alkane of the present invention, is in polar solvent, take imidazoles or pyrimidine as catalyzer, with halogenated silanes, the hydroxyl protection in halohydrin is formed.Its concrete preparation technology is as follows:
250ml four-hole boiling flask is dry more than 10 hours at 120～130 ℃ in air dry oven, load onto while hot normal pressure dropping funnel, spherical condensation tube and mechanical stirring, under argon shield, make it be cooled to room temperature, by halogenated silanes and halohydrin with 1～1.3: 1 amount of substance (mole) than being dissolved in polar solvent, and add in time in four-hole boiling flask, temperature is controlled between-5～5 ℃, by halogenated silanes amount of substance (mole) 80～130% imidazoles or pyrimidine, under argon shield, in 30 minutes, drip, and temperature is risen to 20～50 ℃, and maintain at this temperature and react 4～8 hours, then in system, add the non-polar solvent of 2～5 times of polar solvent volume, then with sodium hydrogen carbonate solution washing, separate non-polar solvent layer, with rotatory evaporator, boil off solvent and obtain Alkylsiloxy-1-halogenated aliphatic alkane solution.
Described chlorosilane is chlorotriethyl silane, tert-butyl diphenyl chlorosilane, tri isopropyl chlorosilane or TERT-BUTYL DIMETHYL CHLORO SILANE etc.Its structure is shown below:
R
1, R
2, R
3for
n is 0～3 integer,
Or R
1, R
2, R
3for
in one or more.
Described halohydrin is halo primary alconol or halo secondary alcohol, as: the chloro-1-ethanol of 2-, trimethylene chlorohydrin, the chloro-n-butyl alcohol of 4-, 1-chloro-2-propanol etc.Its structural formula is:
Wherein X is Cl, Br, I;
R
1for
n is 1～5 integer;
R
2for H or
m is 0～6 integer;
The polar solvent adopting is tetrahydrofuran (THF) or DMF; Non-polar solvent is normal hexane, normal heptane, hexanaphthene or hexahydroaniline.
(3) α, omega end alkyl siloxy polymkeric substance synthetic
α of the present invention, the synthetic method of omega end alkyl siloxy polymkeric substance, to cause diolefine or vinylbenzene formation α-end alkyl siloxy polymer active long-chain with alkyl siloxy aliphatic alkyl lithium, use again the Alkylsiloxy-1-halogenated aliphatic alkane of preparation as terminator, form omega end alkyl siloxy.Finally under acidic conditions, remove blocking group and obtain α, omega end hydroxy polymer.Its concrete preparation technology is as follows:
Under spirit lamp baking, use argon gas/vacuum displacement three times applying argon gas to certain pressure in dried 150ml single port flask, with the needle tubing of same argon gas/vacuum displacement three times, add the solvent after refining after cooling, add in the same way vinylbenzene or isoprene (divinyl adds under-20-10 ℃ condition), the amount of substance of solvent and monomer (mole) than being 4～6: 1, finally with needle tubing, add alkyl siloxy agent with hydroxylic protected by silane, at-80～80 ℃, react after 1～4 hour, add alkyl siloxy alkyl lithium initiator amount of substance (mole) alkyl siloxy halogenated aliphatic alkane doubly of 1-3, at-80～100 ℃, react and when solution is colourless, obtain α, omega end alkyl siloxy polystyrene or α, omega end alkyl siloxy diene polymer solution, again coagulation liquid is gone in acidified solvent blocking group to obtain α, omega end hydroxy polymer.
The present invention is relative, and prior art has the following advantages:
1, the preparation condition of Alkylsiloxy-1-halogenated aliphatic alkane of the present invention is gentle, and technique is simple, and productive rate is high.
2, it is gentle that Alkylsiloxy-1-halogenated aliphatic alkane of the present invention stops α-end alkyl siloxy polymer active chain condition, and effect is remarkable, can not form dimer.Use this terminator both can synthesize the same functional polymer of end, also can form the different functional polymer of end.
3, the α that prepared by the present invention, omega end alkyl siloxy polymkeric substance blocking group silylation is easily removed.
Embodiment
Embodiment 1
250ml four-hole boiling flask is placed in to blast drier and at 250 ℃, is dried 12 hours, constant pressure funnel, spherical condensation tube are installed while hot, mechanical stirrer, and be cooled to room temperature under argon shield, with cold cycle reactive bath technique, provide low-temperature receiver.Successively by 100mlN, dinethylformamide, 38g (0.4mol) trimethylene chlorohydrin and 61g (0.4mol) triethyl chlorosilane add four-hole boiling flask, then will be containing the N of 38g (0.44mol) imidazoles, dinethylformamide (30ml) solution adds in constant pressure funnel, and at 5 ℃, in 30min, dropwise join in reaction system, in ar gas environment, 40 ℃ are stirred 6 hours.Add 350ml hexanaphthene, then wash three times with 5% sodium bicarbonate aqueous solution, separate hexanaphthene layer.With Rotary Evaporators, boil off solvent, through chromatographic column separation, obtain colourless liquid, i.e. triethyl-(3-chlorine propoxy-) silane, productive rate 93%, is placed in the container sealing that fills hydrolith and preserves.
By four the 150ml single port flasks (being furnished with magneton) that indicate 1#, 2#, 3# and 4# after dry argon gas/vacuum displacement three times under spirit lamp baking respectively, and with the 100ml needle tubing after argon gas/vacuum displacement, add the hexanaphthene 50ml after refining respectively, 20ml needle tubing adds the vinylbenzene 10ml after refining, 1ml needle tubing adds initiator triethyl siloxy propyl lithium 1ml, under magnetic agitation, in 50 ℃ of reactions 2 hours, polymer fluid was red-brown.In 1# flask, with 5ml needle tubing, add 2ml methyl alcohol, instaneous polymerization system color is become colorless translucent by red-brown, with dehydrated alcohol cohesion, washing, obtains white powder α-end triethyl siloxy polystyrene after Büchner funnel suction filtration, is designated as 1-1# sample.2#, 3# flask add respectively 2ml triethyl-(3-chlorine propoxy-) silane with 5ml needle tubing, 2# flask is stirring reaction at 50 ℃, 3# flask is stirring reaction at 22 ℃, in 2# flask, polymer fluid was become colorless translucent after 1 hour by red-brown, 5.5 hours post polymerization liquid red-browns of 3# flask are decorporated, and show colourless translucent.With dehydrated alcohol cohesion, washing polymer fluid, obtain white powder α after Büchner funnel suction filtration respectively, omega end triethyl siloxy polystyrene, is designated as respectively 2-1#, 3-1# sample.Respectively get the tetrahydrofuran (THF) that half 2-1#, 3-1# sample are dissolved in respectively concentrated hydrochloric acid acidifying, and at room temperature stir, then with alcohol cohesion, washing, after Büchner funnel suction filtration, obtain white powder α 0.5 hour, omega end hydroxyl polystyrene, is designated as respectively 2-2#, 3-2# sample.In 4# flask, with 5ml needle tubing, add 2ml oxyethane, at 50 ℃, continue reaction 1.5 hours, with 5ml needle tubing, add 2ml methyl alcohol again, dehydrated alcohol cohesion, washing, obtain white powder after Büchner funnel suction filtration, be dissolved in the tetrahydrofuran (THF) after concentrated hydrochloric acid acidifying, stirring at room 30 minutes, then with dehydrated alcohol cohesion, washing, after Büchner funnel suction filtration, obtain white powder α, omega end hydroxyl polystyrene, is designated as 4-1# sample.Molecular weight and distribution gpc analysis thereof, hydroxyl value acetylation reagent chemical titration.The results are shown in Table 1.
Table 1 test result
Embodiment 2
As embodiment mono-installs and the cooling 250ml four-hole boiling flask of argon gas and supporting reinforced, cooling and stirring instrument thereof; add successively 100mlN; dinethylformamide; 38g (0.4mol) 1-chloro-2-propanol and 77g (0.4mol) triisopropyl chlorosilane; 35.2g (0.44mol) pyrimidine is dissolved in 50mlN, dinethylformamide, and add in normal pressure funnel; within 30 minutes at 0 ℃, dropwise add, under argon shield, stirring at room is 6 hours.Add 350ml normal hexane, then use 5% NaHCO3 solution washing three times, separate normal hexane layer.Rotation boils off solvent, through chromatographic column separation, obtains colourless liquid---and be triisopropyl-(3-chlorine propoxy-) silane, productive rate 83%, is placed in the container sealing preservation that fills hydrolith.
By three the 150ml single port flasks (being furnished with magneton) that indicate 1#, 2# and 3# after dry argon gas/vacuum displacement three times under spirit lamp baking respectively, and with the 100ml needle tubing after argon gas/vacuum displacement, add the hexanaphthene 50ml after refining respectively, 20ml needle tubing adds the isoprene 10ml after refining, 1ml needle tubing adds initiator tri isopropyl siloxany propyl lithium 1ml, under magnetic agitation, in 50 ℃ of reactions 2.5 hours, polymer fluid was yellow-green colour.In 1# flask, with 5ml needle tubing, add 2ml methyl alcohol, instaneous polymerization liquid is become colorless translucent by yellow-green colour, with dehydrated alcohol cohesion, washing, obtains colourless α-end tri isopropyl siloxany liquid polyisoprene after vacuum-drying, is designated as 1-1# sample.2#, 3# flask add respectively 2ml triisopropyl-(3-chlorine propoxy-) silane with 5ml needle tubing, 2# flask is stirring reaction at 50 ℃, 3# flask is stirring reaction at 25 ℃, in 2# flask polymer fluid after 2.5 hours by the yellow-green colour transparence that becomes colorless, 7 hours post polymerization liquid yellow-green colours of 3# flask are decorporated, and show colourless translucent.With dehydrated alcohol cohesion, washing polymer fluid, obtain water white transparency shape α after vacuum-drying respectively, omega end tri isopropyl siloxany polyisoprene, is designated as respectively 2-1#, 3-1# sample.Respectively get the tetrahydrofuran (THF) that half is dissolved in respectively concentrated hydrochloric acid acidifying, and at room temperature stir 0.5 hour, then with obtaining water white transparency shape liquid α after alcohol cohesion, washing, vacuum-drying, omega end hydroxyl polyisoprene, is designated as respectively 2-2#, 3-2# sample.Molecular weight and distribution gpc analysis thereof, hydroxyl value acetylation reagent chemical titration.The results are shown in Table 2.
Table 2 test result
Embodiment 3
As embodiment mono-installs and the cooling 250ml four-hole boiling flask of argon gas and supporting reinforced, cooling and stirring instrument thereof; add successively 100mlN; dinethylformamide, 38g (0.4mol) trimethylene chlorohydrin, 60g (0.4mol) tertiary butyl dimethyl chlorosilane; 38g (0.44mol) imidazoles is dissolved in to 50mlN; dinethylformamide; dropwise reaction 30 minutes dropwise at 5 ℃, under argon shield, stirring at room is 12 hours.Add 350ml normal hexane, then wash three times with 5% sodium bicarbonate aqueous solution, separate normal hexane layer.Rotation boils off solvent, through chromatographic column separation, obtains colourless liquid---the tertiary butyl-(3-chlorine propoxy-) dimethylsilane, and productive rate 92%, product is placed in the container sealing preservation that fills hydrolith.
By three 150ml single port flasks (being furnished with magneton) of the dried 1# of indicating, 2# and 3# vacuum/argon replaces three times under spirit lamp baking respectively, and with the 100ml needle tubing after vacuum/argon replaces, add the hexanaphthene 50ml after refining respectively,-20 ℃ add the divinyl 8g after refining, 1ml needle tubing adds initiator tertiary butyl dimethyl Si base propyl lithium 1ml, under magnetic agitation, in 50 ℃ of reactions 2.5 hours, polymer fluid was yellow-green colour.In 1# flask, with 5ml needle tubing, add 2ml methyl alcohol, instaneous polymerization liquid is become colorless translucent by yellow-green colour, with dehydrated alcohol cohesion, washing, obtains colourless α-end tertiary butyl dimethyl Si base liquid polybutadiene after vacuum-drying, is designated as 1-1# sample.2#, 3# flask add respectively the 2ml tertiary butyl-(3-chlorine propoxy-) dimethylsilane with 5ml needle tubing, 2# flask is stirring reaction at 50 ℃, 3# flask is stirring reaction at 25 ℃, in 2# flask polymer fluid after 2.5 hours by the yellow-green colour transparence that becomes colorless, 8 hours post polymerization liquid yellow-green colours of 3# flask are decorporated, and show colourless translucent.With dehydrated alcohol cohesion, washing polymer fluid, obtain water white transparency shape α after vacuum-drying respectively, omega end tertiary butyl dimethyl Si base polyhutadiene, is designated as respectively 2-1#, 3-1# sample.Respectively get the tetrahydrofuran (THF) that half is dissolved in respectively concentrated hydrochloric acid acidifying, and at room temperature stir 0.5 hour, then with alcohol cohesion, washing, obtain water white transparency shape liquid α after vacuum-drying, omega end hydroxyl polyhutadiene, is designated as respectively 2-2#, 3-2# sample.Molecular weight and distribution thereof are measured with GPC, hydroxyl value acetylation reagent chemical titration.The results are shown in Table 3.
Table 3 test result
Embodiment 4
As embodiment mono-installs and the cooling 250ml four-hole boiling flask of argon gas and supporting reinforced, cooling and stirring instrument thereof; add successively 100mlN; dinethylformamide, 38g (0.4mol) trimethylene chlorohydrin, 60g (0.4mol) tertiary butyl dimethyl chlorosilane; 38g (0.44mol) imidazoles is dissolved in to 50mlN; dinethylformamide; at 5 ℃, dropwise drip, in 30 minutes, dropwise, under argon shield, stirring at room is 12 hours.Add 350ml normal hexane, then wash three times with 5% sodium bicarbonate aqueous solution, separate normal hexane layer.Rotation boils off solvent, through chromatographic column separation, obtains colourless liquid---the tertiary butyl-(3-chlorine propoxy-) dimethylsilane, and productive rate 92%, product is placed in the container sealing preservation that fills hydrolith.
By two 150ml single port flasks (being furnished with magneton) of the dried 1# of indicating and 2# argon gas/vacuum displacement three times under spirit lamp baking respectively, and with the 100ml needle tubing after argon gas/vacuum displacement, add the tetrahydrofuran (THF) 50ml after refining respectively, with 50ml needle tubing, add the vinylbenzene 10ml after refining, 1ml needle tubing adds initiator tertiary butyl dimethyl Si base propyl lithium 1ml, be placed in cold cycle reactive bath technique in-78 ℃ of reactions 2.5 hours, polymer fluid is red-brown.In 1# flask, with 5ml needle tubing, add 2ml methyl alcohol, instaneous polymerization liquid is become colorless translucent by red-brown, with dehydrated alcohol cohesion, washing, obtains white powder α-end tertiary butyl dimethyl Si base polystyrene after Büchner funnel suction filtration, is designated as 1-1# sample.2# flask adds the 2ml tertiary butyl-(3-chlorine propoxy-) dimethylsilane with 5ml needle tubing, at-78 ℃ stirring reaction after 6 hours by the red-brown transparence that becomes colorless.With dehydrated alcohol cohesion, washing polymer fluid, after Büchner funnel suction filtration, obtain white powder α, omega end tertiary butyl dimethyl Si base polystyrene, is designated as 2-1# sample.Get the tetrahydrofuran (THF) that half is dissolved in concentrated hydrochloric acid acidifying, and at room temperature stir 0.5 hour, then with alcohol cohesion, washing, obtain white powder α after Büchner funnel suction filtration, omega end hydroxyl polystyrene, is designated as 2-2# sample.Molecular weight and distribution thereof are measured with GPC, hydroxyl value acetylation reagent chemical titration.The results are shown in Table 4.
Table 4 test result
Claims (2)
1. the application of an Alkylsiloxy-1-halogenated aliphatic alkane, it is characterized in that: for α, the terminator that omega end alkyl siloxy polymkeric substance is synthetic, concrete technology is as follows: dried 150ml single port flask is used to argon gas/vacuum displacement three times under spirit lamp baking, with the needle tubing of same argon gas/vacuum displacement three times, add the solvent after refining after cooling, add in the same way monomer styrene or isoprene or add divinyl under-20-10 ℃ condition, the amount of substance of solvent and monomer (mole) than being 4～6:1, finally with needle tubing, add alkyl siloxy alkyl lithium initiator, at-80～80 ℃, react after 1～4 hour, add alkyl siloxy alkyl lithium initiator amount of substance (mole) Alkylsiloxy-1-halogenated aliphatic alkane doubly of 1-3, at-80～100 ℃, react and when solution is colourless, obtain α, omega end alkyl siloxy polystyrene or α, omega end alkyl siloxy diene polymer solution, again coagulation liquid is gone in acidified solvent blocking group to obtain α, omega end hydroxy polymer,
Its molecular structural formula of described Alkylsiloxy-1-halogenated aliphatic alkane is as follows:
R
1, R
2, R
3for: CH
3-[CH
2]-
mor
or
in one or more,
The integer that wherein m is 0～4;
R
4for
Wherein, R
5for
n is 1～5 integer,
R
6for H or
m is 0～6 integer;
X is Cl or Br.
2. the application of Alkylsiloxy-1-halogenated aliphatic alkane according to claim 1, is characterized in that: described acidified solvent is tetrahydrofuran (THF) or DMF.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5708092A (en) * | 1994-05-13 | 1998-01-13 | Fmc Corporation | Functionalized chain extended initiators for anionic polymerization |
| CN1916036A (en) * | 2006-08-17 | 2007-02-21 | 山东大学 | Polymer of terminal dihydroxy, and prepartion method |
| CN101274972A (en) * | 2008-05-01 | 2008-10-01 | 中国石油兰州石油化工公司 | Preparation for low molecular weight hydroxy-terminated polybutadiene |
| CN101274966A (en) * | 2008-05-01 | 2008-10-01 | 中国石油兰州石油化工公司 | Acyclic lithium alkylide evocating agent with hydroxylic protected by silane, preparation thereof and application thereof |
-
2010
- 2010-10-22 CN CN201010522222.1A patent/CN102453047B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5708092A (en) * | 1994-05-13 | 1998-01-13 | Fmc Corporation | Functionalized chain extended initiators for anionic polymerization |
| CN1916036A (en) * | 2006-08-17 | 2007-02-21 | 山东大学 | Polymer of terminal dihydroxy, and prepartion method |
| CN101274972A (en) * | 2008-05-01 | 2008-10-01 | 中国石油兰州石油化工公司 | Preparation for low molecular weight hydroxy-terminated polybutadiene |
| CN101274966A (en) * | 2008-05-01 | 2008-10-01 | 中国石油兰州石油化工公司 | Acyclic lithium alkylide evocating agent with hydroxylic protected by silane, preparation thereof and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Adam J. Meuler等，.Synthesis of Monodisperse α-Hydroxypoly(styrene）in Hydrocarbon Media Using a Functional Organolithium.《Macromolecules》.2007,第40卷(第3期),第760-762页. * |
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