CN100516077C - Preparing method for organic silicon compound containing quaternary ammonium group - Google Patents

Preparing method for organic silicon compound containing quaternary ammonium group Download PDF

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Publication number
CN100516077C
CN100516077C CNB2007100134237A CN200710013423A CN100516077C CN 100516077 C CN100516077 C CN 100516077C CN B2007100134237 A CNB2007100134237 A CN B2007100134237A CN 200710013423 A CN200710013423 A CN 200710013423A CN 100516077 C CN100516077 C CN 100516077C
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quaternary ammonium
ammonium group
organic silicon
silicon compound
silicoorganic compound
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CN101016310A (en
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李俊英
宋增峰
李天铎
杨鹏飞
张萌
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Shandong Institute of Light Industry
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Shandong Institute of Light Industry
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Abstract

The invention discloses a making method of organic silicon compound with little-surface tension quaternary ammonium group, which is characterized by the following: reacting (RO)2CH3Si(CH2)3X and secondary amine to produce organic silicon compound with tertiary amino; reacting with halogenated alkyl to do quaternised reaction; making the organic silicon compound with structure as (RO)2CH3Si(CH2)3N+R1R2R3X-; fitting for surface activator of organic silicon cation, sterilizer and antibacterial agent; lengthening sterilizing time.

Description

The preparation method who contains the silicoorganic compound of quaternary ammonium group
Technical field:
The present invention relates to a kind of preparation method, relate in particular to a kind of preparation method who contains the silicoorganic compound of quaternary ammonium group, belong to field of fine chemical with chemical of sterilization, germ resistance
Background technology:
At present sterilization, the antiseptic-germicide kind of using is more, uses wider cats product and be mostly alkyl quaternary ammonium salts, but its chemically reactive is low, with the bonding force of application a little less than, loss easily.And its toxicity is relatively large, is subjected to certain limitation.And the organosilicon cationic tensio-active agent can combine with object by chemical bond in application because of its special structure, has persistence, and because of organosilyl physiology inertia, makes its toxicity reduce greatly.
1967, first developed the U.S. Dowcorning company organosilicon quaternary ammonium salt DC-5700 and has applied for patent.Molecular structure is [(CH 3O) 3Si (CH 2) 3N +(CH 3) 2C 18H 37] Cl -Methoxyl group hydrolyzable wherein becomes hydroxyl, forms chemical bond with textiles and combines the firm surface that is adsorbed on textiles.This product is well received since throwing in market, but its synthetic method complexity, price is higher, has limited its consumption.Therefore the research of the type product is being carried out always.
The Yezhong just respect and wait [Yezhong is just respected and is waited. the will .1975 of Japanization association] to be main raw material with dialkylamine, allyl halide and containing hydrogen silicone oil obtained four kinds of organic silicon surfactants that contain quaternary ammonium group by multistep is synthetic suddenly, studied the effect of they throwing outs when handling papermaking sewage and Kaolin clay suspension, the result is satisfactory.
Zhou Yupeng etc. [high-grade meticulous and 2000 the 17th phases of specialty chemicals of shampoo-conditioner of Zhou Yupeng polysiloxane quaternary ammonium] generate polyether-modified polysiloxane through hydrosilation reaction with containing hydrogen silicone oil, unsaturated ethers under the platinum catalyst effect, then with monochloroacetic acid fatization under catalyst action, carry out quaterisation with tertiary amine again, use it for high-grade shampoo-conditioner, have the hair soft of making smooth, antistatic, preserve moisture, good comprehensive performances such as antibiotic.
Huang Zuoxin etc. [Huang is made the complex functionality polymer journal Vol.132000 No.4 in December that prosperous yellow English has the polysiloxane of benzyl dimethyl γ-silicon propyl ammonium chloride side group] use trimethylchlorosilane, the cohydrolysis of dimethyldichlorosilane(DMCS) and γ-chloropropyl dimethyl dichlorosilane (DMCS) and sulfuric acid catalysis equilibration reaction have been synthesized the end capped γ of trimethylammonium silica-chloropropyl methylsiloxane dimethylsiloxane copolymer, multipolymer and N, the quaterisation of N-dimethyl benzyl amine has synthesized the polysiloxane that has benzyl dimethyl γ-silicon propyl ammonium chloride side group, and this product all has good antibacterial to intestinal bacteria and streptococcus aureus, sterilization effect.
Chinese patent 02134372.1 has been reported a kind of preparation method of organosilicon quaternary ammonium salt polymer, make with the polysiloxane and other silicone monomers condensation copolymerization that contain tackify group such as amino again behind reaction 0.5～24h down at 70～140 ℃ by the organoalkoxysilane that has γ-halogen propyl group and tertiary amine, with fabric, hair viscosifying power is preferably arranged, multiple Gram-positive, negative bacterium there are killing action, fabric, hair are had good soft effect.
Chinese patent 200510045294.0 has been reported a kind of preparation method of organosilicon quaternary ammonium salt sterilant, dimethyl 18 tertiary amines are dissolved in the ethanol of dehydration fully, slowly drip γ-chloropropyl triethoxysilane again, make after the temperature reaction under catalyzer exists.Can be used for the fabric sterilant, the indoor environment sterilant.
Prior preparation method, the one, in reaction, to use expensive platinum catalyst or other catalyzer, the 2nd, reactions steps is more, and aftertreatment is trouble.
Summary of the invention:
At the deficiencies in the prior art, the problem to be solved in the present invention provides the method that a kind of preparation contains the silicoorganic compound of quaternary ammonium group, and this method has been simplified reactions steps, has increased the application performance of product.
Below in detail technical scheme of the present invention will be described in detail:
The preparation method who contains the silicoorganic compound of quaternary ammonium group of the present invention can realize by following reaction process:
(RO) 2CH 3Si(CH 2) 3X+HNR 1R 2→(RO) 2CH 3Si(CH 2) 3NR 1R 2+HX·HNR 1R 2
(RO) 2CH 3Si(CH 2) 3NR 1R 2+R 3X→(RO) 2CH 3Si(CH 2) 3N +R 1R 2R 3X -
The first step is mixed secondary amine with organosilicon halogenide, be warming up to 50～130 ℃, preferred 80～120 ℃, reaction system pressure normal pressure is to 0.6MPa, preferred 0.3～0.5MPa, 8～24 hours reaction times, preferred 10～18 hours, the mol ratio of organosilicon halogenide and secondary amine is 1: 2～6, preferred 1: 3～4, after reaction is finished, the secondary amine halate is filtered out, filtrate is obtained containing the silicoorganic compound (RO) of tertiary amine groups after conventional underpressure distillation 2CH 3Si (CH 2) 3NR 1R 2
Second step is with (RO) 2CH 3Si (CH 2) 3NR 1R 2With R 3X mixes in the presence of inert solvent, is warming up to 45～100 ℃, is preferably 60～90 ℃, in 2～24 hours reaction times, is preferably 6～12 hours, (RO) 2CH 3Si (CH 2) 3NR 1R 2With R 3The mol ratio of X is 1: 1～2, be preferably 1: 1.0～and 1.2, (RO) 2CH 3Si (CH 2) 3N R 1R 2With the weight ratio of inert solvent be 1: 1～2, obtain containing the silicoorganic compound (RO) of quaternary ammonium group 2CH 3Si (CH 2) 3N +R 1R 2R 3X -Solution.
Preparation method of the present invention can also comprise the silicoorganic compound (RO) to containing quaternary ammonium group 2CH 3Si (CH 2) 3N +R 1R 2R 3X -Further purification etc.
Wherein R is methyl or ethyl, R 1, R 2, R 3Be identical or different alkyl, be selected from methyl, ethyl, benzyl, epoxypropyl, X is selected from Cl or Br
Described inert solvent is a kind of in anhydrous methanol, ethanol, propyl alcohol, the epoxy chloropropane or their mixture.
The compound that can prepare by this method has:
(CH 3O) 2CH 3Si(CH 2) 3N +(CH 3) 2C 6H 5Cl -、
(CH 3O) 2CH 3Si(CH 2) 3N +(CH 3) 2CH 2CHOCH 2Cl -
(CH 3O) 2CH 3Si(CH 2) 3N +(CH 3) 2C 6H 5Br -、
(CH 3O) 2CH 3Si(CH 2) 3N +(CH 3) 2CH 2CHOCH 2Br -
(CH 3O) 2CH 3Si(CH 2) 3N +(C 2H 5) 2C 6H 5Cl -、
(CH 3O) 2CH 3Si(CH 2) 3N +(C 2H 5) 2CH 2CHOCH 2Cl -
(CH 3O) 2CH 3Si(CH 2) 3N +(C 2H 5) 2C 6H 5Br -、
(CH 3O) 2CH 3Si(CH 2) 3N +(C 2H 5) 2CH 2CHOCH 2Br -
(C 2H 5O) 2CH 3Si(CH 2) 3N +(CH 3) 2C 6H 5Cl -、
(C 2H 5O) 2CH 3Si(CH 2) 3N +(CH 3) 2CH 2CHOCH 2Cl -
(C 2H 5O) 2CH 3Si(CH 2) 3N +(CH 3) 2C 6H 5Br -、
(C 2H 5O) 2CH 3Si(CH 2) 3N +(CH 3) 2CH 2CHOCH 2Br -
(C 2H 5O) 2CH 3Si(CH 2) 3N +(C 2H 5) 2C 6H 5Cl -、
(C 2H 5O) 2CH 3Si(CH 2) 3N +(C 2H 5) 2CH 2CHOCH 2Cl -
(C 2H 5O) 2CH 3Si(CH 2) 3N +(C 2H 5) 2C 6H 5Br -、
(C 2H 5O) 2CH 3Si(CH 2) 3N +(C 2H 5) 2CH 2CHOCH 2Br -
The silicoorganic compound that contain quaternary ammonium group of the present invention can be used as sterilization, antiseptic-germicide uses, and are applicable in daily necessities or the fabric finishing agent.
Compared with prior art, the present invention has following advantage:
1. the employing low price raw material is simplified reaction scheme, does not use catalyzer in the reaction
2. introduce functional group, strengthen the product bonding properties with reactive behavior
3. product of the present invention has stronger sterilization, germ resistance, and usefulness is lasting
4. product can directly be used, and also can utilize the characteristic of alkoxyl group and epoxy group(ing), prepares other compound as intermediate product
Description of drawings:
Accompanying drawing 1 contains the silicoorganic compound of quaternary ammonium group for embodiment 3 synthetic 1The H-NMR spectrogram, CD 3OD is a deuterated reagent.
Accompanying drawing 2 contains the silicoorganic compound of quaternary ammonium group for embodiment 7 synthetic 1The H-NMR spectrogram, CD 3OD is a deuterated reagent.
Embodiment
Will the invention will be further elaborated in the following examples, but the invention is not restricted to this.
Embodiment 1
With 90g (CH 3O) 2CH 3Si (CH 2) 3Cl and 200g diethylamine add in the exsiccant reactor, are heated to 105 ℃ under stirring, and pressure is 0.3～0.4Mpa, react to stir after 10 hours and reduce to room temperature, feed liquid is filtered, and the air distillation of filtrate elder generation is again through (71～72 ℃/4mmHg) obtain 50g intermediate product (CH of underpressure distillation 3O) 2CH 3Si (CH 2) 3N (C 2H 5) 2
Embodiment 2
With 45ml (CH 3O) 2CH 3Si (CH 2) 3Cl and the adding of 150ml diethylamine are equipped with in the four-hole bottle of stirring, thermometer, reflux condensing tube and nitrogen protection device; be heated with stirring to 60 ℃ under the normal pressure; react to stir after 20 hours and reduce to room temperature; feed liquid is filtered; the air distillation of filtrate elder generation is again through (101～109 ℃/30mmHg) obtain 12g intermediate product (CH of underpressure distillation 3O) 2CH 3Si (CH 2) 3N (C 2H 5) 2
Embodiment 3
In the four-hole bottle that thermometer, reflux condensing tube, dropping funnel and nitrogen protection device are housed, add (the CH that 10.95g is obtained by embodiment 2 3O) 2CH 3Si (CH 2) 3N (C 2H 5) 2With the 30g anhydrous methanol, be warming up to 55 ℃ under the induction stirring, slow Dropwise 5 .6g epoxy chloropropane reacts and promptly got the silicoorganic compound (CH that contains quaternary ammonium group in 4 hours 3O) 2CH 3Si (CH 2) 3N +(C 2H 5) 2CH 2CHOCH 2Cl -Methanol solution, distillation for removing methanol, with anhydrous diethyl ether washing for several times the final vacuum drying obtain faint yellow transparent quaternary ammonium salt product, recording chloride ion content through silver nitrate titration is 90.12%, oxirane value is 70.99%.
Accompanying drawing 1 is this compound 1The H-NMR spectrogram, corresponding chemical shift is respectively: 0.419ppm is-Si-C H 3The peak, the triplet at 0.974ppm place is-Si-C H 2-C peak, 1.648ppm is-C-C H 2-C-peak, 1.151ppm is-N +-C-C H 3The peak, 3.293ppm is Si-O-C H 3The peak, 3.410ppm is CH 3-C H 2-N +-methylene peak, 3.180ppm is C-C H 2-N +-peak, 3.500ppm is the methyne absorption peak that links to each other with epoxide group, the 2.800ppm place is the absorption peak of the methylene radical that links to each other with epoxy.
Embodiment 4
In the four-hole bottle that thermometer, reflux condensing tube, dropping funnel and nitrogen protection device are housed, add (the CH that 8.5g is obtained by embodiment 2 3O) 2CH 3Si (CH 2) 3N (C 2H 5) 2With the 20ml anhydrous methanol, be heated to 65 ℃ under the induction stirring, slowly drip the 6.7ml Benzyl Chloride, react and promptly got the silicoorganic compound (CH that contains quaternary ammonium group in 22 hours 3O) 2CH 3Si (CH 2) 3N +(C 2H 5) 2C 6H 5Cl -Methanol solution 15.6g, it is 30.36% that nonaqueous titration records quaternary ammonium salt content.
Embodiment 5
In the four-hole bottle that thermometer, reflux condensing tube, dropping funnel and nitrogen protection device are housed, add (the CH that 15.00g is obtained by embodiment 1 3O) 2CH 3Si (CH 2) 3N (C 2H 5) 2With the 30.00g dehydrated alcohol, be warming up to 45 ℃ under the induction stirring, slowly drip the 8.34g epoxy chloropropane, react and promptly got the silicoorganic compound (CH that contains quaternary ammonium group in 6 hours 3O) 2CH 3Si (CH 2) 3N +(C 2H 5) 2CH 2CHOCH 2Cl -Methanol solution, distillation for removing methanol, with anhydrous diethyl ether washing for several times the final vacuum drying obtain faint yellow transparent quaternary ammonium salt product, recording chloride ion content through silver nitrate titration is 60.59%, oxirane value is 50.38%.
Embodiment 6
In the four-hole bottle that thermometer, reflux condensing tube, dropping funnel and nitrogen protection device are housed, add (the CH that 5.14g is obtained by embodiment 1 3O) 2CH 3Si (CH 2) 3N (C 2H 5) 2With 20 anhydrous methanols, be warming up to 50 ℃ under the induction stirring, slowly drip the 4.00g epoxy chloropropane, react and promptly got the silicoorganic compound (CH that contains quaternary ammonium group in 8 hours 3O) 2CH 3Si (CH 2) 3N +(C 2H 5) 2CH 2CHOCH 2Cl -Methanol solution, distillation for removing methanol, with anhydrous diethyl ether washing for several times the final vacuum drying obtain faint yellow transparent quaternary ammonium salt product, recording chloride ion content through silver nitrate titration is 50.69%, oxirane value is 70.94%.
Embodiment 7
In the four-hole bottle that thermometer, reflux condensing tube, dropping funnel and nitrogen protection device are housed, add 15.0ml Benzyl Chloride and 10ml dehydrated alcohol, be heated to 80 ℃ under the induction stirring, slowly drip (the CH that 10g is obtained by embodiment 1 3O) 2CH 3Si (CH 2) 3N (C 2H 5) 2, react and promptly got the silicoorganic compound (CH that contains quaternary ammonium group in 15 hours 3O) 2CH 3Si (CH 2) 3N +(C 2H 5) 2C 6H 5Cl -Ethanolic soln 20g, it is 70.44% that nonaqueous titration records quaternary ammonium salt content.
Accompanying drawing 2 is this compound 1The H-NMR spectrogram, corresponding chemical shift is respectively: 0.05ppm is-Si-C H 3The peak, the triplet at 0.975 place is-N +-C-C H 3The peak, 1.23ppm is Si-C H 2-C-peak, 1.70ppm is Si-C-C H 2-C-peak, 3.10ppm is and N +The methene proton peak that links to each other, 3.30ppm is Si-O-C H 3The peak, 7.33ppm is the phenyl ring proton peak
Embodiment 8
In the four-hole bottle that thermometer, reflux condensing tube, dropping funnel and nitrogen protection device are housed, add (the CH that 5.50g is obtained by embodiment 1 3O) 2CH 3Si (CH 2) 3N (C 2H 5) 2With the 15ml dehydrated alcohol, be heated to 75 ℃ under the induction stirring, slowly drip the 3.0ml Benzyl Chloride, react and promptly got the silicoorganic compound (CH that contains quaternary ammonium group in 18 hours 3O) 2CH 3Si (CH 2) 3N +(C 2H 5) 2C 6H 5Cl -Ethanolic soln 12.40g, it is 30.68% that nonaqueous titration records quaternary ammonium salt content.

Claims (2)

1. contain the preparation method of the silicoorganic compound of quaternary ammonium group, it is characterized in that, described preparation method is as follows:
(1) with (RO) 2CH 3Si (CH 2) 3X and secondary amine are at 50～130 ℃, and normal pressure～0.6MPa reacted 8～24 hours, (RO) 2CH 3Si (CH 2) 3The mol ratio of X and secondary amine is 1: 2～6, filters earlier after reaction is finished, and filtrate obtains containing the silicoorganic compound (RO) of tertiary amine groups after conventional underpressure distillation 2CH 3Si (CH 2) 3N R 1R 2, described secondary amine is HR 1R 2
(2) with (RO) 2CH 3Si (CH 2) 3N R 1R 2With R 3X is warming up to 45～100 ℃ in the presence of inert solvent, reacted 2～24 hours, (RO) 2CH 3Si (CH 2) 3N R 1R 2With R 3The mol ratio of X is 1: 1～2, obtains containing the silicoorganic compound (RO) of quaternary ammonium group 2CH 3Si (CH 2) 3N +R 1R 2R 3X -Solution;
Wherein R is methyl or ethyl, R 1, R 2Be selected from methyl, ethyl, benzyl, R 3Be epoxypropyl, X is selected from Cl or Br.
2. preparation method according to claim 1 is characterized in that, described inert solvent is a kind of in anhydrous methanol, ethanol, the propyl alcohol or their mixture.
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