CN109912801A - One kind siloxanes of functional poly containing quaternary ammonium salt and its synthetic method - Google Patents
One kind siloxanes of functional poly containing quaternary ammonium salt and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of siloxanes of functional poly containing quaternary ammonium salt and its synthetic method, this contain quaternary ammonium salt functional poly siloxanes its with structural formula shown in formula (I): in formula (I), R is hydroxyl, vinyl or alkoxy；R1For any one of substituted or unsubstituted straight chained alkyl, branched alkyl, aryl, aralkyl or benzyl；R2For quaternary ammonium salt.Using brine alkyl methyl alkoxy silane and tertiary amine as raw material, solvent, nitrogen protection is added, heating reaction obtains alkoxy silane monomer containing quaternary ammonium salt；Prepared alkoxy silane monomer containing quaternary ammonium salt is mixed with hydroxyl-terminated injecting two methyl siloxane, catalyst is added, inert gas shielding, heating reaction is in atmospheric conditions to get the siloxanes of functional poly containing quaternary ammonium salt.The siloxanes of functional poly containing quaternary ammonium salt of the present invention, preparation method is simple, and yield is high, and molecular weight is controllable, and post-processing is simple, and production cost reduces, easy large-scale production.
Description
Technical field
The present invention relates to a kind of polysiloxanes and preparation method thereof, more particularly to a kind of silicon oxygen of functional poly containing quaternary ammonium salt
Alkane and preparation method thereof belongs to functional polymer research field.
Background technique
Organosilicon polymer due to having the special molecular structure and composition of Si-O-Si main chain and organic side chain, tool simultaneously
There are unique excellent properties, such as resistance to oxidation, chemicals-resistant, electrical isolation, radiation hardness, weather-proof, hydrophobic, fire-retardant, salt spray resistance, mould proof
Deng；The characteristics of having high molecular material easy processing concurrently simultaneously can be made according to different requirements and meet product for various purposes.
Polysiloxanes achieves very rapid development in recent years, and a series of functional polyorganosiloxanes with special construction exist
Great success is all achieved in laboratory research and industrial production.It is original that functional polyorganosiloxane not only remains polysiloxane
Excellent properties, while impart again its by the other special natures of functional group's bring or using functional group activity with it is other
New material is constructed in compound reaction.
Quaternary ammonium salt functional group is introduced in polysiloxane molecule chain, so that polysiloxanes has antibiotic property, before can be used as
Drive the preparation that body is used for anti-biotic material.In the prior art, the preparation method in relation to the functional polyorganosiloxane containing quaternary ammonium salt mainly has:
1, R. H. Liza et al. is by amido silicon oil and epoxypropyltrimethylchloride chloride (or the chloro- 2- hydroxypropyl dimethyl 12 of 3-
Alkyl ammomium chloride, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride) reaction, obtain quaternized polysiloxanes；2, M. Partha etc.
People makees catalyst with platinum, by containing hydrogen silicone oil and allyl dimethyl base amine in toluene solvant, in 60 DEG C of progress hydrosilylations
16h obtains tertiary amino silicone oil；Quaternization reaction 48h is carried out with 1- iodo-octane at room temperature again, obtains polysiloxanes containing quaternary ammonium salt；3,
J. Chojnowski et al. synthesizes halogen hydrocarbyl polysiloxane, then utilizes quaternization reaction, and polysiloxanes is quaternized, obtains
To the polysiloxanes containing quaternary ammonium salt.Above all multi-methods are then drawn on polysiloxane chain by first synthesizing polysiloxanes
Enter quaternary ammonium salt group, that there are product yields is low, experimental implementation is difficult, it is difficult to industrialize, contain especially for high molecular weight is obtained
Quaternary ammonium salt polysiloxanes is particularly difficult.
Summary of the invention
In view of the deficiencies of the prior art, the problem to be solved in the present invention is to provide a kind of siloxanes of functional poly containing quaternary ammonium salt
And its synthetic method.
The siloxanes of functional poly containing quaternary ammonium salt of the present invention, which is characterized in that it is with structural formula shown in formula (I):
(I)
In formula (I), R is hydroxyl, vinyl or alkoxy；
R1For any one of substituted or unsubstituted straight chained alkyl, branched alkyl, aryl, aralkyl or benzyl；
R2For quaternary ammonium salt；
M=0 ~ 5000, n=1 ~ 500, k=1 ~ 100, m and n are all integer；
The number-average molecular weight of the siloxanes of functional poly containing quaternary ammonium salt is Mn=1 × 103~3×105。
, according to the invention it is preferred to, in formula (I), m+n=100 ~ 5000, n/m=0.0001 ~ 0.1；It is further preferred that
n/m=0.0005~0.05。
, according to the invention it is preferred to, number-average molecular weight Mn=5 × 10 of the siloxanes of functional poly containing quaternary ammonium salt3~3×
105。
According to the present invention, the preparation method of the siloxanes of functional poly containing quaternary ammonium salt, comprises the following steps that
(1) preparation of the alkoxy silane monomer containing quaternary ammonium salt: in the reactor be added brine alkyl methyl alkoxy silane, tertiary amine and
Solvent is heated to solvent refluxing under nitrogen protection, and reaction time 24-72h, after completion of the reaction, cooled to room temperature depressurizes
Distillation removing low-boiling-point substance, obtains the liquid of yellow transparent oily, and three times with petroleum ether product, vacuum drying for 24 hours, is contained
Quaternary ammonium salt alkoxy silane monomer.Wherein, the brine alkyl methyl alkoxy silane is chloropropyl diethoxy silane, chlorine
Hydroxypropyl methyl dimethoxysilane, chloromethyl methyldiethoxysilane, chloromethyl-methyl-dimethylsilane or it is other containing
The alkoxy silane of brine alkyl；The tertiary amine is N, N- dimethyl n octylame, N, N- dimethyl dodeca-tertiary amine, N, N- dimethyl ten
Four tertiary amines, N, 16 tertiary amine of N- dimethyl, N, 18 tertiary amine of N- dimethyl, pyridine structure contained compound, containing glyoxaline structure
Compound or other compounds containing tertiary amine structure；The solvent be methanol, ethyl alcohol, N,N-dimethylformamide, n-butanol,
Any weight ratio assembles between dimethyl sulfoxide, acetonitrile or these solvents；
(2) R is the preparation of the siloxanes of functional poly containing quaternary ammonium salt of hydroxyl: with alkoxy silane monomer containing quaternary ammonium salt and terminal hydroxy group
Dimethyl silicone polymer is raw material, be added catalyst, inert gas shielding, be warming up in atmospheric conditions 70 ~ 130 DEG C reaction 4 ~
12h removes catalyst after reaction, is warming up to 130 ~ 200 DEG C, vacuumizes removing low-boiling-point substance, is cooled to room temperature, and obtained R is
The siloxanes of functional poly containing quaternary ammonium salt of hydroxyl；Wherein, the catalyst is potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethyl
The silicon alkoxide of base ammonium hydroxide or these alkaline matters.
(3) R be vinyl the siloxanes of functional poly containing quaternary ammonium salt preparation: with alkoxy silane monomer containing quaternary ammonium salt with
Hydroxyl-terminated injecting two methyl siloxane is raw material, and end-capping reagent is added, adds catalyst, inert gas shielding, in atmospheric conditions
It is warming up to 70 ~ 130 DEG C of 4 ~ 12h of reaction and removes catalyst after reaction, be warming up to 130 ~ 200 DEG C, vacuumize removing low boiling
Object is cooled to room temperature, and the siloxanes of functional poly containing quaternary ammonium salt that R is vinyl is made；Wherein, the end-capping reagent is tetramethyl two
Vinyl disiloxane；The catalyst is potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide or these alkali
The silicon alkoxide of property substance.
(4) R is the preparation of the siloxanes of functional poly containing quaternary ammonium salt of alkoxy: being hydroxyl containing quaternary ammonium salt by the R of preparation
Functional poly siloxanes sequentially adds alkoxy end-capped dose, catalyst, is warming up to 50 ~ 110 DEG C, and insulation reaction 1-8h is obtained
R is the siloxanes of functional poly containing quaternary ammonium salt of alkoxy；Wherein, described alkoxy end-capped dose is tetramethoxy-silicane, methyl three
Methoxy silane, methyltriethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane；The catalyst
For organo-tin compound, alkali metal hydroxide, fatty sodium alkoxide, silanol potassium, organic guanidine, tetramethylammonium hydroxide or contain oximido
Close object.
Further preferred embodiment is:
(1) preparation of the alkoxy silane monomer containing quaternary ammonium salt: in the reactor be added brine alkyl methyl alkoxy silane, tertiary amine and
Solvent is heated to solvent refluxing under nitrogen protection, and 36 ~ 72h of reaction time, after completion of the reaction, cooled to room temperature depressurizes
Distillation removing low-boiling-point substance, obtains the liquid of yellow transparent oily, and three times with petroleum ether product, vacuum drying for 24 hours, is contained
Quaternary ammonium salt alkoxy silane monomer.Wherein, the brine alkyl methyl alkoxy silane be chloropropyl diethoxy silane or
Chloropropylmethyldimethoxysilane；The tertiary amine is N, N- dimethyl n octylame or pyridine；The solvent be methanol, ethyl alcohol,
N,N-dimethylformamide；
(2) R is the preparation of the siloxanes of functional poly containing quaternary ammonium salt of hydroxyl: with alkoxy silane monomer containing quaternary ammonium salt and terminal hydroxy group
Dimethyl silicone polymer is raw material, be added catalyst, inert gas shielding, be warming up in atmospheric conditions 90 ~ 110 DEG C reaction 8 ~
10h removes catalyst after reaction, is warming up to 150 ~ 180 DEG C, vacuumizes removing low-boiling-point substance, is cooled to room temperature, and obtained R is
The siloxanes of functional poly containing quaternary ammonium salt of hydroxyl；Wherein, number-average molecular weight Mn=1 of the hydroxyl-terminated injecting two methyl siloxane ×
103~5×104, the catalyst is tetramethylammonium hydroxide silicon alkoxide.
(3) R be vinyl the siloxanes of functional poly containing quaternary ammonium salt preparation: with alkoxy silane monomer containing quaternary ammonium salt with
Hydroxyl-terminated injecting two methyl siloxane is raw material, and end-capping reagent is added, adds catalyst, inert gas shielding, in atmospheric conditions
It is warming up to 90 ~ 110 DEG C of 8 ~ 10h of reaction and removes catalyst after reaction, be warming up to 150 ~ 180 DEG C, vacuumize removing low boiling
Object is cooled to room temperature, and the siloxanes of functional poly containing quaternary ammonium salt that R is vinyl is made；Wherein, the end-capping reagent is tetramethyl two
Vinyl disiloxane；The catalyst is tetramethylammonium hydroxide silicon alkoxide.
(4) R is the preparation of the siloxanes of functional poly containing quaternary ammonium salt of alkoxy: being hydroxyl containing quaternary ammonium salt by the R of preparation
Functional poly siloxanes sequentially adds alkoxy end-capped dose, catalyst, is warming up to 90 ~ 110 DEG C, and 6 ~ 8h of insulation reaction is obtained
R is the siloxanes of functional poly containing quaternary ammonium salt of alkoxy；Wherein, described alkoxy end-capped dose is methyltrimethoxysilane or second
Alkenyl triethoxysilane；The catalyst is cyclohexanone oxime or tetramethylammonium hydroxide.
According to the present invention, alkoxy silane monomer containing quaternary ammonium salt described in step (2) and (3) is prepared in step (1).
According to the present invention, the hydroxyl-terminated injecting two methyl siloxane has following structure formula:
(II)
In formula (II), m=0 ~ 8000, it is preferred that m=30 ~ 2000.
The principle of the present invention:
By the way that quaternization reaction occurs between the chlorocarbon base and tertiary amine in the silane monomer of methyl alkoxy containing brine alkyl, obtain containing season
Ammonium salt alkoxy silane monomer；Then the alkoxy silane monomer containing quaternary ammonium salt of synthesis and hydroxyl-terminated injecting two methyl siloxane are existed
Polymerization reaction occurs under catalyst, the siloxanes of functional poly containing quaternary ammonium salt is made.
The advantages of the present invention:
The siloxanes of functional poly containing quaternary ammonium salt of the present invention, preparation method is simple, and yield is high, and molecular weight is controllable, post-processing letter
Single, production cost reduces, easy large-scale production.
The present invention can obtain the controllable functional poly siloxanes of quaternary ammonium salt content, and can obtain by the dosage of control raw material
The siloxanes of functional poly containing quaternary ammonium salt for the sub- amount that secures satisfactory grades.
Specific embodiment
For a better understanding of the present invention, below with reference to embodiment, technical scheme is described further, but
Institute's protection scope of the present invention is not limited to the range of embodiment statement.
In embodiment it is raw materials used unless otherwise specified, be regular market purchase product.
Embodiment 1
In the single-necked flask equipped with spherical condensation tube and magneton, sequentially add 5.27g chloropropyl diethoxy silane,
3.93gN, N- dimethyl n octylame and 7.5ml ethyl alcohol, stirring are uniformly mixed it, nitrogen protection, and 48h is reacted in 80 DEG C of reflux,
After reaction, vacuum distillation removes low-boiling-point substance, obtains the liquid of yellow transparent oily, three times with petroleum ether product, very
Sky is dry for 24 hours, as Quaternary Ammonium Functional Methyldiethoxysilane monomer (I), yield 97%.
In the three-necked flask for being furnished with spherical condensation tube, thermometer, blender, 3.00g methyl diethoxy is sequentially added
Organosilane quaternary ammonium salt monomer (I), 30.10g hydroxyl-terminated injecting two methyl siloxane (number-average molecular weight Mn=5860) and 0.33g tetramethyl
Ammonium hydroxide silicon alkoxide, stirring are uniformly mixed it, and nitrogen protection is to slowly warm up to 70 DEG C of holding 0.5h, then raises temperature to 100
DEG C, 10h is reacted, by system 130 DEG C of holding 0.5h of heating, then vacuum distillation removes low-boiling-point substance, obtains pale yellow transparent oily
Liquid, as R are the siloxanes of functional poly containing quaternary ammonium salt of hydroxyl, yield 95%.
Embodiment 2
In the single-necked flask equipped with spherical condensation tube and magneton, sequentially add 5.27g chloropropyl diethoxy silane,
3.93gN, N- dimethyl n octylame and 7.5ml ethyl alcohol, stirring are uniformly mixed it, nitrogen protection, and 48h is reacted in 80 DEG C of reflux,
After reaction, vacuum distillation removes low-boiling-point substance, obtains the liquid of yellow transparent oily, three times with petroleum ether product, very
Sky is dry for 24 hours, as Quaternary Ammonium Functional Methyldiethoxysilane monomer (I), yield 97%.
In the three-necked flask for being furnished with spherical condensation tube, thermometer, blender, 3.00g methyl diethoxy is sequentially added
Organosilane quaternary ammonium salt monomer (I), 30.10g hydroxyl-terminated injecting two methyl siloxane (number-average molecular weight Mn=5860), 0.10g tetramethyl two
Vinyl disiloxane and 0.33g tetramethylammonium hydroxide silicon alkoxide, stirring are uniformly mixed it, and nitrogen protection slowly heats up
To 70 DEG C of holding 0.5h, 100 DEG C are then raised temperature to, reacts 10h, then system 130 DEG C of holding 0.5h of heating are evaporated under reduced pressure
Low-boiling-point substance is removed, pale yellow transparent oily liquids is obtained, as R is the siloxanes of functional poly containing quaternary ammonium salt of vinyl, yield
It is 93%.
Embodiment 3
In the single-necked flask equipped with spherical condensation tube and magneton, sequentially add 3.86g chloromethyl-methyl-dimethylsilane,
3.94gN, N- dimethyl n octylame and 7.5ml ethyl alcohol, stirring are uniformly mixed it, nitrogen protection, and 48h is reacted in 80 DEG C of reflux,
After reaction, vacuum distillation removes low-boiling-point substance, obtains the liquid of yellow transparent oily, three times with petroleum ether product, very
Sky is dry for 24 hours, as methyl dimethoxysilane quaternary ammonium salt monomer (II), yield 99%.
In the three-necked flask for being furnished with spherical condensation tube, thermometer, blender, 3.00g methyl dimethoxy oxygroup is sequentially added
Organosilane quaternary ammonium salt monomer (II), 25.12g hydroxyl-terminated injecting two methyl siloxane (number-average molecular weight Mn=5860) and 0.28g tetramethyl
Ammonium hydroxide silicon alkoxide, stirring are uniformly mixed it, and nitrogen protection is to slowly warm up to 70 DEG C of holding 0.5h, then raises temperature to 100
DEG C, 10h is reacted, by system 130 DEG C of holding 0.5h of heating, then vacuum distillation removes low-boiling-point substance, obtains pale yellow transparent oily
Liquid, as R are the siloxanes of functional poly containing quaternary ammonium salt of hydroxyl, yield 92%.
Embodiment 4
In the single-necked flask equipped with spherical condensation tube and magneton, sequentially add 3.86g chloromethyl-methyl-dimethylsilane,
3.94gN, N- dimethyl n octylame and 7.5ml ethyl alcohol, stirring are uniformly mixed it, nitrogen protection, and 48h is reacted in 80 DEG C of reflux,
After reaction, vacuum distillation removes low-boiling-point substance, obtains the liquid of yellow transparent oily, three times with petroleum ether product, very
Sky is dry for 24 hours, as methyl dimethoxysilane quaternary ammonium salt monomer (II), yield 99%.
In the three-necked flask for being furnished with spherical condensation tube, thermometer, blender, 3.00g methyl dimethoxy oxygroup is sequentially added
Organosilane quaternary ammonium salt monomer (II), 25.12g hydroxyl-terminated injecting two methyl siloxane (number-average molecular weight Mn=5860), 0.08g tetramethyl
Divinyl disiloxane and 0.28g tetramethylammonium hydroxide silicon alkoxide, stirring are uniformly mixed it, and nitrogen protection slowly rises
Temperature then raises temperature to 100 DEG C, reacts 10h, by system 130 DEG C of holding 0.5h of heating, then decompression is steamed to 70 DEG C of holding 0.5h
Low-boiling-point substance is removed in distillation, obtains pale yellow transparent oily liquids, and as R is the siloxanes of functional poly containing quaternary ammonium salt of vinyl, produces
Rate is 88%.
Embodiment 5
As described in Example 1, by the N of quaternization reaction unlike, N- dimethyl n octylame is changed to pyridine.
Embodiment 6
As described in Example 1, the etoh solvent of quaternization reaction is changed to n,N-Dimethylformamide unlike.
Embodiment 7
As described in Example 1, change the dosage of each raw material in copolyreaction, i.e. 3.00g methyldiethoxysilane unlike
Quaternary ammonium salt monomer (I), 60.52g hydroxyl-terminated injecting two methyl siloxane (number-average molecular weight Mn=5860) and 0.63g tetramethyl hydrogen-oxygen
Change ammonium silicon alkoxide.
Embodiment 8
As described in Example 1, the tetramethylammonium hydroxide silicon alkoxide in copolyreaction is changed to potassium hydroxide unlike.
Embodiment 9
As described in Example 1, the molecular weight for changing hydroxyl-terminated injecting two methyl siloxane unlike, i.e., by terminal hydroxy group poly dimethyl
The number-average molecular weight of siloxanes is changed to Mn=10750 by Mn=5860.
Embodiment 10
As described in Example 2, by the N of quaternization reaction unlike, N- dimethyl n octylame is changed to imidazoles.
Embodiment 11
As described in Example 2, the etoh solvent of quaternization reaction is changed to n,N-Dimethylformamide unlike.
Embodiment 12
As described in Example 2, change the dosage of each raw material in copolyreaction, i.e. 1.55g methyldiethoxysilane unlike
Quaternary ammonium salt monomer (I), 51.53g hydroxyl-terminated injecting two methyl siloxane (number-average molecular weight Mn=5860), 0.10g tetramethyl divinyl
Base disiloxane and 0.53g tetramethylammonium hydroxide silicon alkoxide.
Embodiment 13
As described in Example 2, the tetramethylammonium hydroxide silicon alkoxide in copolyreaction is changed to potassium hydroxide unlike.
Embodiment 14
As described in Example 2, the molecular weight for changing hydroxyl-terminated injecting two methyl siloxane unlike, i.e., by terminal hydroxy group poly dimethyl
The molecular weight of siloxanes is changed to 10750 by 5860.
Embodiment 15
In three-necked flask, the hydroxy-end capped polysiloxanes containing quaternary ammonium salt of 100g obtained in embodiment 1 is added, is warming up to 80 DEG C,
2g methyltrimethoxysilane and 0.5g cyclohexanone oxime are sequentially added, 3h is reacted, vacuum takes off low boiling after reaction, and obtaining R is
The siloxanes of functional poly containing quaternary ammonium salt of alkoxy, yield 98%.
Embodiment 16
As described in Example 15, methyltrimethoxysilane is changed to vinyltriethoxysilane unlike.
Embodiment 17
As described in Example 15, cyclohexanone oxime is changed to tetramethylammonium hydroxide unlike.
Claims (5)
1. a kind of siloxanes of functional poly containing quaternary ammonium salt, which is characterized in that it is with structural formula shown in formula (I):
(I)
In formula (I), R is hydroxyl, vinyl or alkoxy；
R1For any one of substituted or unsubstituted straight chained alkyl, branched alkyl, aryl, aralkyl or benzyl；
R2For quaternary ammonium salt；
M=0 ~ 5000, n=1 ~ 500, k=1 ~ 100, m and n are all integer；
Number-average molecular weight Mn=1 × 10 of the siloxanes of functional poly containing quaternary ammonium salt3~3×105。
2. the siloxanes of functional poly containing quaternary ammonium salt according to claim 1, which is characterized in that in formula (I), m+n=100 ~
5000, n/m=0.0001 ~ 0.1.
3. the preparation method of the siloxanes of functional poly containing quaternary ammonium salt described in claim 1, step is:
(1) preparation of the alkoxy silane monomer containing quaternary ammonium salt: in the reactor be added brine alkyl methyl alkoxy silane, tertiary amine and
Solvent is heated to solvent refluxing under nitrogen protection, and 24 ~ 72h of reaction time, after completion of the reaction, cooled to room temperature depressurizes
Distillation removing low-boiling-point substance, obtains the liquid of yellow transparent oily, and three times with petroleum ether product, vacuum drying for 24 hours, is contained
Quaternary ammonium salt alkoxy silane monomer；Wherein, the brine alkyl methyl alkoxy silane is chloropropyl diethoxy silane, chlorine
Hydroxypropyl methyl dimethoxysilane, chloromethyl methyldiethoxysilane, chloromethyl-methyl-dimethylsilane or it is other containing
The alkoxy silane of brine alkyl；The tertiary amine is N, N- dimethyl n octylame, N, N- dimethyl dodeca-tertiary amine, N, N- dimethyl ten
Four tertiary amines, N, 16 tertiary amine of N- dimethyl, N, 18 tertiary amine of N- dimethyl, pyridine structure contained compound, containing glyoxaline structure
Compound or other compounds containing tertiary amine structure；The solvent be methanol, ethyl alcohol, N,N-dimethylformamide, n-butanol,
Any weight ratio assembles between dimethyl sulfoxide, acetonitrile or these solvents；
(2) R is the preparation of the siloxanes of functional poly containing quaternary ammonium salt of hydroxyl: with alkoxy silane monomer containing quaternary ammonium salt and terminal hydroxy group
Dimethyl silicone polymer is raw material, be added catalyst, inert gas shielding, be warming up in atmospheric conditions 70 ~ 130 DEG C reaction 4 ~
12h removes catalyst after reaction, is warming up to 130 ~ 200 DEG C, vacuumizes removing low-boiling-point substance, is cooled to room temperature, and obtained R is
The siloxanes of functional poly containing quaternary ammonium salt of hydroxyl；Wherein, the catalyst is potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethyl
The silicon alkoxide of base ammonium hydroxide or these alkaline matters；
(3) R is the preparation of the siloxanes of functional poly containing quaternary ammonium salt of vinyl: with alkoxy silane monomer containing quaternary ammonium salt and end hydroxyl
Base dimethyl silicone polymer is raw material, and end-capping reagent is added, adds catalyst, inert gas shielding heats up in atmospheric conditions
Catalyst is removed after reaction to 70 ~ 120 DEG C of 4 ~ 12h of reaction, 130 ~ 200 DEG C is warming up to, vacuumizes removing low-boiling-point substance, it is cold
But to room temperature, the siloxanes of functional poly containing quaternary ammonium salt that R is vinyl is made；Wherein, the end-capping reagent is tetramethyl divinyl
Base disiloxane；The catalyst is potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide or these basic species
The silicon alkoxide of matter；
(4) R is the preparation of the siloxanes of functional poly containing quaternary ammonium salt of alkoxy: being the salt functional containing quaternary ammonium of hydroxyl by the R of preparation
Change polysiloxanes, sequentially adds alkoxy end-capped dose, catalyst, be warming up to 50 ~ 110 DEG C, 1 ~ 8h of insulation reaction, obtaining R is
The siloxanes of functional poly containing quaternary ammonium salt of alkoxy；Wherein, described alkoxy end-capped dose is tetramethoxy-silicane, methyl trimethoxy oxygen
Base silane, methyltriethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane；The catalyst is to have
Machine tin compound, alkali metal hydroxide, fatty sodium alkoxide, silanol potassium, organic guanidine, tetramethylammonium hydroxide or chemical combination containing oximido
Object.
4. the preparation method of the siloxanes of functional poly containing quaternary ammonium salt according to claim 3, which is characterized in that step (2) and
(3) alkoxy silane monomer containing quaternary ammonium salt is prepared in step (1).
5. the preparation method of the siloxanes of functional poly containing quaternary ammonium salt according to claim 3, which is characterized in that the terminal hydroxy group
Dimethyl silicone polymer has following structure formula:
(II)
In formula (II), m=0 ~ 8000, it is preferred that m=30 ~ 2000.
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|---|---|---|---|---|
| CN109897185A (en) * | 2019-03-18 | 2019-06-18 | 山东交通学院 | A kind of side chain is containing vinyl and quaternary ammonium salt polysiloxanes and its synthetic method and the application in preparation antibacterial silicon rubber |
| CN111269660A (en) * | 2020-02-04 | 2020-06-12 | 刘涛 | Self-adhesive antibacterial silicone rubber and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4417066A (en) * | 1981-10-03 | 1983-11-22 | Dow Corning Limited | Siloxane quaternary ammonium salt preparation |
| CN1468887A (en) * | 2002-07-17 | 2004-01-21 | 黄振宏 | Prepn and application of organosilicon quaternary ammonium salt polymer |
| WO2007120173A2 (en) * | 2005-08-11 | 2007-10-25 | Auburn University | N-halamine/quaternary ammonium polysiloxane copolymers |
| CN104558006A (en) * | 2013-10-17 | 2015-04-29 | 上海才水泉实业有限公司 | Quaternary ammonium silane and preparation method thereof |
| CN108586751A (en) * | 2018-05-16 | 2018-09-28 | 山东交通学院 | A kind of ethenyl blocking polysiloxanes containing quaternary ammonium salt and its synthesis and the application in preparing intrinsic quaternary antibacterial silicon rubber |
-
2019
- 2019-03-18 CN CN201910201282.4A patent/CN109912801A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4417066A (en) * | 1981-10-03 | 1983-11-22 | Dow Corning Limited | Siloxane quaternary ammonium salt preparation |
| CN1468887A (en) * | 2002-07-17 | 2004-01-21 | 黄振宏 | Prepn and application of organosilicon quaternary ammonium salt polymer |
| WO2007120173A2 (en) * | 2005-08-11 | 2007-10-25 | Auburn University | N-halamine/quaternary ammonium polysiloxane copolymers |
| CN104558006A (en) * | 2013-10-17 | 2015-04-29 | 上海才水泉实业有限公司 | Quaternary ammonium silane and preparation method thereof |
| CN108586751A (en) * | 2018-05-16 | 2018-09-28 | 山东交通学院 | A kind of ethenyl blocking polysiloxanes containing quaternary ammonium salt and its synthesis and the application in preparing intrinsic quaternary antibacterial silicon rubber |
Non-Patent Citations (2)
| Title |
|---|
| 何卫东等编: "《高分子化学实验 第2版》", 30 September 2012, 合肥：中国科学技术大学出版社 * |
| 黄文润编著: "《液体硅橡胶》", 30 June 2009, 成都：四川科学技术出版社 * |
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| CN111269660A (en) * | 2020-02-04 | 2020-06-12 | 刘涛 | Self-adhesive antibacterial silicone rubber and preparation method thereof |
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