CN101045759A - Styrene or substituted styrene polymer type quaternary ammonium salt antistat or bacterial agent and preparation method thereof - Google Patents
Styrene or substituted styrene polymer type quaternary ammonium salt antistat or bacterial agent and preparation method thereof Download PDFInfo
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Abstract
This invention relates a (substituting) styrene polymer type quaternary ammonium salt anti-static agent or germicide and preparation method. ( substituting)styrene homopolymerization or copolymerization with comonomer form straight chain polymer, take fu-ke reaction with oxirane in fine solvent, introduce ethoxyl to benzene ring of straight chain polymer, then use proper halogenating agent for halogenation, form Alpha - halogenation ethyl, then takes reaction with tertiary amine, thereby form quaternary ammonium salt that molecular weight about 400 to 200000. This macromolecule quaternary ammonium salt could form macromolecule permanent type anti-static agent or germicide, used in antistatic as well as sterilization of PVC, PP, PE, ABS and such on molecule stuff.
Description
Technical field
The present invention relates to static inhibitor or sterilant field, particularly relate to (replacement) styrene polymer type quaternary ammonium salt static inhibitor or sterilant and preparation method thereof.
Background technology
Macromolecular material has the excellent comprehensive performance, is widely used in fields such as communications and transportation, electric, national defense industry.But the macromolecular material volume specific resistance is very big, in use easily produces and be with static, has potential hazard.Antistatic macromolecule material is along with the increasingly extensive of polymer application scope grows up.Because polymkeric substance is the good insulation performance material mostly, be occasions such as the plastics, fiber, rubber etc. of matrix can't be applied to prevent dust, explosion-proof with them.In order to change this situation, eliminate the harm that static brought, begin both at home and abroad to develop obtaining antistatic polymer compounds and obtain remarkable progress.Static inhibitor is that a class is added on resin or coats polymer surface to prevent or to eliminate the chemical additive of generation of static electricity, and adding static inhibitor is the effective ways that improve the polymer surface specific conductivity.That common static inhibitor has is cationic, anionic, non-ionic type, amphoteric ion type, permanent polymer.Wherein, the macromole of cation quaternary ammonium salt type also has germ-resistant effect, can be used for sterilant simultaneously.
Many hydrophilic polymers are better relatively and stable lasting owing to its antistatic usefulness, and are called as " permanent " static inhibitor.Their degree of scatter and dispersion staties in the matrix polymer have remarkably influenced to the matrix resin antistatic property.Hydrophilic polymer after lower shearing force stretches, is fine muscle shape at the matrix macromolecule surface in the presence of special compatilizer, i.e. stratiform dispersed texture, and centre portions is then near spherical distribution.The stratiform dispersion state of the hydrophilic polymer in this " stamen shell " structure can reduce blends surface resistance effectively, and has permanent antistatic performance, and for example common permanent antistatic agent is
The permanent antistatic agent that table 1 is common
| Classification | Title | Be suitable for resin |
| Polyethers | Poly-epoxy hexane (PEO) | PS |
| Polyether ester amides | PP、ABS | |
| Polyetheramides imide (PEEA) | PS、HIPS、ABS、MBS、AS | |
| PEOBCH (propylene chlorohydrin) | PVC、ABS、AS | |
| PEG (methyl) methyl acrylate copolymer | PMMA | |
| Quaternary ammonium salt | Contain quaternary ammonium salt base propylene ester copolymer | PS、AS、ABS、PVC |
| Contain the quaternary ammonium salt base maleimide copolymer | ABS | |
| Contain quaternary ammonium salt base methacrylic imide copolymer | PMMA | |
| Other | Sodium polystyrene sulfonate | ABS |
| Salt copolymer in the quaternary ammonium carboxylic acid | PP、PE | |
| Charge transfer type polymer coupler thing | PP、PE、PVC |
The permanent polymeric antistatic agent of above-mentioned these still has many weak points, and for example the consistency with resin is good, on the high side inadequately, and the resin that is suitable for is extensive inadequately or the like.
Summary of the invention
The objective of the invention is to overcome the deficiency that above-mentioned prior art exists, be engaged in the development research of polymeric antistatic agent, sterilant for many years through the contriver, better with resin compatible, that antistatic effect is excellent, sterilization effect good, pungency is low, economical and practical (replacement) styrene polymer type quaternary ammonium salt static inhibitor or sterilant and preparation method thereof are developed in the investigation of the production practice and the market requirement.
(replacement) provided by the invention vinylbenzene (referring to vinylbenzene or substituted phenylethylene) polymer-type quaternary ammonium salt static inhibitor or sterilant is characterized in that its chemical structural formula is:
Wherein X be can be styrene copolymerized with (replacement) monomer (hereinafter to be referred as comonomer), be ethene, propylene, divinyl, isoprene, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid-α-hydroxyl ethyl ester, senecioate-hydroxyl ethyl ester, the vinylformic acid hydroxy butyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid-α-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, the methacrylic acid hydroxy butyl ester, MALEIC ANHYDRIDE or vinyl cyanide, wherein comonomer X can be one or more comonomers, forms binary or multi-component copolymer compound; N is 2 to 200 integers, form (replacement) the vinylbenzene homopolymerization of different number n or the mixture of multipolymer, wherein comonomer is 1: 10 to 10: 1 with (replacement) cinnamic molar ratio, if comonomer adopts two or more, and available any ratio; M is 1,2 or 3 integer, at the ortho position of phenyl ring and/or contraposition form the quaternary ammonium salt of 1 to 3 replacement; The R substituting group is a hydrogen, methyl, ethyl, chloromethyl, brooethyl, methylol, halogen, nitro, phenyl, benzyl, methoxyl group, oxyethyl group, tert.-butoxy, methylthio group, ethylmercapto group, rosickyite base, thiophenyl, to methylbenzene sulfenyl, carboxyl, methoxycarbonyl, ethoxy carbonyl, propenyloxy group carbonyl, metacryloxy carbonyl or sulfonic group; The Y negative ion is the gegenion of quaternary ammonium salt in the formula, is chlorion, bromide anion; R
1, R
2And R
3Be respectively C
1～C
24Alkyl, methyl for example, ethyl, propyl group such as sec.-propyl and n-propyl, isobutyl-, normal-butyl, isopentyl, n-pentyl, the hexyl heptyl, octyl group, appoint base, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, the isooctadecane base, eicosyl, docosyl, tetracosyl, benzyl, tallow, the h-tallow base, cocoyl, the hydrogenation cocoyl, oil base, the guar gum hydroxypropyl, poly-propoxy-, the butter amido-ethyl, the isostearoyl aminocarbonyl propyl, the Viscotrol C amidopropyl, vinyl pyrrolidone-methacryloyl amido propyl group or alkyl imidazoline base, R
1, R
2And R
3Can be identical or different, eight above alkyl of carbon atom can only have one simultaneously and be present in the molecule; On the main chain of (replacement) styrene polymer molecular chain, grafting 1-3n contains quaternary ammonium moiety, forms the mixture of molecular weight 400-200000.
What of contained halogen number on the main chain according to (replacement) styrene polymer molecular chain, the quaternary ammonium salt group of grafting respective number, thereby form (replacement) styrene polymer type quaternary ammonium salt static inhibitor or the fungicide mixture of molecular weight 400-200000, so have the consistency of resin better, and its electric density can regulate and control, and application prospect is widely arranged.
(replacement) provided by the invention styrene polymer type quaternary ammonium salt static inhibitor or sterilant preparation method comprise the following steps:
(1) preparation of polymkeric substance
In the band stirred vessel of organic solvent such as hexanaphthene or ethylene dichloride etc. is housed, in the presence of benzoyl peroxide or Diisopropyl azodicarboxylate, in 50-90 ℃ of adding (replacement) vinylbenzene, comonomer, reaction times 0.5-6 hour, the molar ratio of control benzoyl peroxide or Diisopropyl azodicarboxylate and (replacement) vinylbenzene, comonomer is 0.002: 1 to 0.1: 2, and obtaining molecular weight is 400-50000, (replacement) styrene homopolymers or the multipolymer of n=2-200; Perhaps by (replacement) vinylbenzene, with comonomer in the presence of organolithium, carry out anionoid polymerization, preparation (replacement) styrene homopolymers or multipolymer, it is 0.0025: 1 to 0.25: 1 that the basic lithium and the molar ratio of (replacement) vinylbenzene, comonomer are wherein arranged; Comonomer is 1: 10 to 10: 1 with (replacement) cinnamic mol ratio;
(2) ethoxylation and halogenation
In having the container of stirring, add step (1) gained (replacement) styrene homopolymers or multipolymer, and add the good solvent of (replacement) styrene homopolymers or multipolymer, under 0-100 ℃, add the Lewis acid such as the AlCl of catalytic amount
3, ZnCl
2, FeCl
3, SnCl
4, BF
3Deng.Feed oxyethane then, wherein the molar ratio of oxyethane and polymkeric substance is: 0.1: 1 to 3: 1; Use the dilute hydrochloric acid hydrolysate again, and wash organic layer with water, use the anhydrous magnesium sulfate drying organic layer.Filter to remove siccative, with organic phase be transferred to have stir and the container of hydrogen halide absorption unit in and add halogenating agent such as PCl
3, PCl
5, SOCl
2, PBr
3, PBr
5Wherein halogenating agent and oxyethane mol ratio are 1: 1, at 50 ℃ to reflux temperature, reacted 1-10 hour, cooling, reactant successively is neutralized to neutrality with rare aqueous sodium hydroxide solution, washes with water then, anhydrous sodium sulfate drying steams the halogenide that can obtain (replacement) styrene homopolymers or multipolymer after desolventizing.
(3) quaternized
In having the container of stirring, the halogenide that adds step (2) gained (replacement) styrene homopolymers or multipolymer, and the halid good solvent of adding (replacement) vinylbenzene homopolymerization or multipolymer, and corresponding tertiary amine, the amount mol ratio of halogen is 1: 1 on wherein said tertiary amine and (replacement) styrene homopolymers or the multipolymer, in room temperature to 250 ℃ reaction after 2-48 hour, press filtration, filter cake washes twice with the mixture of a small amount of solvent and water, drying can get white (replacement) styrene polymer type quaternary ammonium salt static inhibitor or sterilant.
In (replacement) provided by the invention styrene polymer type quaternary ammonium salt static inhibitor or sterilant and preparation method thereof, described (replacement) styrene polymer comprises the homopolymer or the multipolymer of vinylbenzene or substituted phenylethylene.Described substituted phenylethylene is vinyl toluene, ethyl styrene, propylstyrene, isopropyl benzene ethene, 1-chloro-4-methyl-benzene, brooethyl vinylbenzene, chloro-styrene, bromstyrol, propenyloxy group carbonyl styrene or metacryloxy carbonyl styrene.With (replacement) vinylbenzene homopolymerization or with linearity (straight chain) polymkeric substance (comprising homopolymer or multipolymer) of copolymerization monomer copolymerization gained be parent, on linear main polymer chain, introduce quaternary ammonium salt functional group, promptly by on the main polymer chain phenyl ring by ethoxylation, the macromole static inhibitor or the sterilant of halogenation and quaternized introducing quaternary ammonium salt functional group are polymerization degree differences, contain the quaternary ammonium salt structure of functional groups, the percentage of grafting difference, molecular weight has the macromole static inhibitor of antistatic property and bactericidal property or the mixture of sterilant from 400-200000, it is limited to solve existing polymer static inhibitor and resin compatible, occur easily being separated, range of application is narrow, the technical barrier that consumption is big, and the macromole type static inhibitor provided by the invention energy that also has microbe killing properties.Described (replacement) styrene polymer parent comprises molecular weight from 400 to 50000, polymerization degree n=2 to 200 (replacement) vinylbenzene homopolymerization or with the mixture of copolymerization monomer copolymerization gained homopolymer or multipolymer, preferred (replacement) vinylbenzene homopolymer of vinylbenzene, vinyl toluene, ethyl styrene, 1-chloro-4-methyl-benzene, chloro-styrene or bromstyrol for example, or with multipolymer such as random copolymers, segmented copolymer or the alternating copolymer etc. of ethene, propylene, divinyl, isoprene, vinyl cyanide.Described quaternary ammonium salt functional group is in preparation process, select the tertiary amine of appropriate amount for use according to the content of halogen on the polymkeric substance, finally can grafting 1-3n quaternary ammonium salt functional moieties, thereby form high polymer type static inhibitor, the sterilant of molecular weight 400 to 200000, it has excellent antistatic and sterilization effect.Wherein said halogen is preferably chlorine and bromine; Described tertiary amine for example is: Trimethylamine 99, triethylamine, dimethyl amine, methyl-diethyl-amine, dimethyl benzylamine, diethyl benzylamine, 12～tetracosyl dimethylamine, 12～tetracosyl diethylamine, 12～tetracosyl methylbenzylamine, 12～tetracosyl ethyl benzyl amine, 12～tetracosyl methylethyl amine, 12～tetracosyl dimethyl hydroxyethyl amine, 12～tetracosane ylmethyl hydroxypropyl amine, alkyl ethyl-hydroxyethyl amine in 12～20,12～tetracosyl ethyl hydroxypropyl amine, the tallow dimethylamine, the tallow diethylamine, the tallow methylbenzylamine, the tallow ethyl benzyl amine, tallow methylethyl amine, tallow dimethyl hydroxyethyl amine, tallow methyl hydroxypropyl amine, tallow ethyl-hydroxyethyl amine, tallow ethyl hydroxypropyl amine, h-tallow base dimethylamine, h-tallow base diethylamine, h-tallow ylmethyl benzylamine, h-tallow base ethyl benzyl amine, h-tallow ylmethyl ethylamine, h-tallow ylmethyl ethylol amine, h-tallow ylmethyl hydroxypropyl amine, h-tallow base ethyl-hydroxyethyl amine, h-tallow base ethyl hydroxypropyl amine, the cocoyl dimethylamine, the cocoyl diethylamine, the cocoyl methylbenzylamine, the cocoyl ethyl benzyl amine, cocoyl methylethyl amine, cocoyl dimethyl hydroxyethyl amine, cocoyl methyl hydroxypropyl amine, cocoyl ethyl-hydroxyethyl amine, cocoyl ethyl hydroxypropyl amine, hydrogenation cocoyl dimethylamine, hydrogenation cocoyl diethylamine, hydrogenation cocoyl methylbenzylamine, hydrogenation cocoyl ethyl benzyl amine, hydrogenation cocoyl methylethyl amine, hydrogenation cocoyl dimethyl hydroxyethyl amine, hydrogenation cocoyl methyl hydroxypropyl amine, hydrogenation cocoyl ethyl-hydroxyethyl amine, hydrogenation cocoyl ethyl hydroxypropyl amine, the oil base dimethylamine, the oil base diethylamine, the oil base methylbenzylamine, the oil base ethyl benzyl amine, oil base methylethyl amine, oil base dimethyl hydroxyethyl amine, oil base methyl hydroxypropyl amine, oil base ethyl-hydroxyethyl amine, oil base ethyl hydroxypropyl amine, guar gum hydroxypropyl dimethylamine, guar gum hydroxypropyl diethylamine, guar gum hydroxypropylmethyl benzylamine, guar gum hydroxypropyl ethyl benzyl amine, guar gum hydroxypropylmethyl ethylamine, guar gum hydroxypropylmethyl ethylol amine, guar gum hydroxypropylmethyl hydroxypropyl amine, guar gum hydroxypropyl ethyl-hydroxyethyl amine, guar gum hydroxypropyl ethyl hydroxypropyl amine, poly-propoxy-dimethylamine, poly-propoxy-diethylamine, poly-propoxy-methylbenzylamine, poly-propoxy-ethyl benzyl amine, poly-propoxy-methylethyl amine, poly-propoxy-dimethyl hydroxyethyl amine, poly-propoxy-methyl hydroxypropyl amine, poly-propoxy-ethyl-hydroxyethyl amine, poly-propoxy-ethyl hydroxypropyl amine, butter amido-ethyl dimethylamine, butter amido-ethyl diethylamine, butter amido-ethyl methylbenzylamine, butter amido-ethyl ethyl benzyl amine, butter amido-ethyl methylethyl amine, butter amido-ethyl dimethyl hydroxyethyl amine, butter amido-ethyl methyl hydroxypropyl amine, butter amido-ethyl ethyl-hydroxyethyl amine, butter amido-ethyl ethyl hydroxypropyl amine, isostearoyl aminocarbonyl propyl dimethylamine, isostearoyl aminocarbonyl propyl diethylamine, isostearoyl aminocarbonyl propyl methylbenzylamine, isostearoyl aminocarbonyl propyl ethyl benzyl amine, isostearoyl aminocarbonyl propyl methylethyl amine, isostearoyl aminocarbonyl propyl dimethyl hydroxyethyl amine, isostearoyl aminocarbonyl propyl methyl hydroxypropyl amine, isostearoyl aminocarbonyl propyl ethyl-hydroxyethyl amine, isostearoyl aminocarbonyl propyl ethyl hydroxypropyl amine, Viscotrol C amidopropyl dimethylamine, Viscotrol C amidopropyl diethylamine, Viscotrol C amidopropyl methylbenzylamine, Viscotrol C amidopropyl ethyl benzyl amine, Viscotrol C amidopropyl methylethyl amine, Viscotrol C amidopropyl dimethyl hydroxyethyl amine, Viscotrol C amidopropyl methyl hydroxypropyl amine, Viscotrol C amidopropyl ethyl-hydroxyethyl amine, Viscotrol C amidopropyl ethyl hydroxypropyl amine, vinyl pyrrolidone-methacryloyl amido propyl group dimethylamine, vinyl pyrrolidone-methacryloyl amido propyl group diethylamine, vinyl pyrrolidone-methacryloyl amido propyl group methylbenzylamine, vinyl pyrrolidone-methacryloyl amido propyl group ethyl benzyl amine, vinyl pyrrolidone-methacryloyl amido propyl group methylethyl amine, vinyl pyrrolidone-methacryloyl amido propyl group dimethyl hydroxyethyl amine, vinyl pyrrolidone-methacryloyl amido propyl group methyl hydroxypropyl amine, vinyl pyrrolidone-methacryloyl amido propyl group ethyl-hydroxyethyl amine, vinyl pyrrolidone-methacryloyl amido propyl group ethyl hydroxypropyl amine, methyl or ethyl imidazol(e) quinoline base dimethylamine, methyl or ethyl imidazol(e) quinoline base diethylamine, methyl or ethyl imidazol(e) quinoline ylmethyl benzylamine, methyl or ethyl imidazol(e) quinoline base ethyl benzyl amine, methyl or ethyl imidazol(e) quinoline ylmethyl ethylamine, methyl or ethyl imidazol(e) quinoline ylmethyl ethylol amine, methyl or ethyl imidazol(e) quinoline ylmethyl hydroxypropyl amine, methyl or ethyl imidazol(e) quinoline base ethyl-hydroxyethyl amine, methyl or ethyl imidazol(e) quinoline base ethyl hydroxypropyl amine.Described (replacement) vinylbenzene is vinyl toluene, ethyl styrene, propylstyrene, isopropyl benzene ethene, 1-chloro-4-methyl-benzene, brooethyl vinylbenzene, chloro-styrene, bromstyrol, propenyloxy group carbonyl styrene or metacryloxy carbonyl styrene, vinyl toluene, ethyl styrene, propylstyrene, isopropyl benzene ethene; Described comonomer is ethene, propylene, divinyl, isoprene, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid-α-hydroxyl ethyl ester, senecioate-hydroxyl ethyl ester, vinylformic acid hydroxy butyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid-α-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid hydroxy butyl ester, MALEIC ANHYDRIDE or vinyl cyanide, is preferably ethene, propylene, divinyl, isoprene, methyl acrylate, methyl methacrylate, butyl methacrylate or vinyl cyanide; Described organolithium is lithium ethide, propyl lithium, n-Butyl Lithium, isobutyl-lithium, phenyl lithium, naphthalene lithium, the two lithiums of divinyl or the two lithiums of isoprene.
According to the different application field, select different quaternary ammonium salt functional moieties to obtain various (replacement) styrene polymer (macromole) type static inhibitor with antistatic and sterilization effect.
(replacement) provided by the invention styrene polymer type quaternary ammonium salt static inhibitor or sterilant and preparation method's characteristics are:
1, high polymer type static inhibitor of the present invention or sterilant are in the polymkeric substance building-up process, the ratio of may command monomer and initiator, thereby form molecular weight 400-200000, n=2-200 can satisfy (replacement) styrene polymer type static inhibitor or the sterilant of the antistatic of different materials or sterilization demand.
2, high polymer type static inhibitor of the present invention or sterilant are in the polymkeric substance building-up process, can select different comonomers and (replacement) vinylbenzene to form multipolymer, and the ratio of may command comonomer, so that the consistency of macromolecular material is formulated to the best.
3, the present invention can the grafting different types of structure on Molecularly Imprinted Polymer type static inhibitor or sterilant and the quaternary ammonium salt group of number, thereby make antistatic, sterilization effect is excellent and can regulate and control according to demand, cooperate molecular weight and comonomer kind and the ratio on chain again, can make antistatic effect reach best.
Embodiment
The present invention further specifies the present invention with the following example, but protection scope of the present invention is not limited to embodiment.Can make many other variation and modifications in the case of without departing from the spirit and scope of protection of the present invention to those skilled in the art, still be included in the scope of protecting in claims.
The preparation of embodiment 1, poly-Alpha-Methyl (2 (4)-α-chloroethyl) vinylbenzene dimethyl cetyltrimethyl ammonium straight-chain polymer
Get 1 of exsiccant polymerizing pipe, mix the short Glass tubing of single hole soft rubber ball and exsiccant and one section exsiccant rubber tubing, be connected in the anhydrous and oxygen-free operating system, vacuumize, applying argon gas, three times repeatedly, to get rid of air in the test tube.Connect argon system then, with ice bath polymerizing pipe is cooled to 0 ℃, inject 9ml anhydrous cyclohexane and 4.0g exsiccant alpha-methyl styrene and 5.4ml n-Butyl Lithium (2.8M) solution by syringe respectively from rubber tubing, shake up, solution becomes orange, after stirring 30min, add the small amount of methanol termination reaction, color disappears immediately.Reaction solution is dropped in the methyl alcohol of 30ml, the adularescent precipitation generates immediately, filters, and uses the methanol wash after drying, gets white poly alpha methylstyrene 3.7g, yield 92%.
Have in the container of stirring at 50ml, add the poly alpha methylstyrene 3g of step (1) gained, and add chloroform 25ml, at room temperature, add the 0.4g aluminum chloride, slowly feed oxyethane 1.2g then, led in about 3 hours.The dilute hydrochloric acid hydrolysis that adds 5ml 5% in reaction mixture, behind the branch vibration layer, organic layer is used anhydrous sodium sulfate drying with after a spot of water washing three times.Dried organic phase is added 50ml have in the container of stirring and bromize hydrogen gas absorption unit, drip the 3.5g phosphorus trichloride under refluxing, 4 hours times spent are till no hydrogen chloride gas is overflowed.Reactant elder generation divides three washings with 5% sodium bicarbonate aqueous solution 20ml, and then washs with less water, and anhydrous sodium sulfate drying can obtain poly-Alpha-Methyl (2 (4)-chloroethyl) vinylbenzene 3.5g, yield 76% after steaming desolventizes.
Be furnished with at 50ml and add above-mentioned poly-Alpha-Methyl (2 (4)-chloroethyl) vinylbenzene 1.8g, 28ml acetone and 3.2g in the there-necked flask of whipping appts and made with extra care the hexadecyl dimethylamine.Stirring makes all materials be dissolved into homogeneous system, leaves standstill under the room temperature 24 hours, filters, precipitate water and acetone mixture washed twice with 1: 1, drying can get poly-Alpha-Methyl (2 (4)-chloroethyl) the vinylbenzene dimethyl cetyltrimethyl ammonium straight-chain polymer of 3.7g white, and yield is 76%.
The preparation of embodiment 2, poly--2 (4)-chloroethyl vinylbenzene diethyl dodecyl ammonium straight-chain polymers
To being furnished with agitator, having the separating funnel of calcium chloride tube and be connected with in the 2L there-necked flask of the reflux exchanger that absorbs gas device, add the 650ml ethylene dichloride, stir and add 36g benzoyl peroxide and 200g vinylbenzene down again, be warming up to about 5 hours of 60 ℃ of reactions, obtain poly styrene polymer solution.Be cooled to 30 ℃, in reaction flask, add the 26g aluminum chloride.Slowly feed oxyethane 44g then, led in about 5 hours.The dilute hydrochloric acid hydrolysis that adds 80ml 5% in reaction mixture, behind the branch vibration layer, organic layer is used anhydrous sodium sulfate drying with after a spot of water washing three times.Dried organic phase is added 2L have in the container of stirring and bromize hydrogen gas absorption unit, drip the 120g sulfur oxychloride under refluxing, 6 hours times spent are till no hydrogen chloride gas is overflowed.Reactant elder generation divides three washings with 5% sodium bicarbonate aqueous solution 90ml, and then wash with less water, anhydrous sodium sulfate drying, after filtering the removal drying machine, the organic layer adding is furnished with in the 2L container of agitator, and adding 242g dodecyl diethylamine, warming while stirring to 50 ℃, make it dissolving after, continue to stir 10 hours, be cooled to room temperature, filter then, precipitate with a small amount of ethylene dichloride washed twice, drying, can get poly--2 (4)-chloroethyl vinylbenzene diethyl dodecyl ammonium straight-chain polymers of 322g white, yield 71%.
The preparation of embodiment 3, poly-α-ethyl (2 (4)-chloroethyl) styrene-acrylonitrile TMA (TriMethylAmine) straight-chain block copolymer
Get 1 of exsiccant polymerizing pipe, mix single hole soft rubber ball and short Glass tubing and one section rubber tubing, connect in the anhydrous and oxygen-free operating system, vacuumize, applying argon gas, three times repeatedly, to get rid of air in the test tube.Connect argon system then, with ice bath polymerizing pipe is cooled to 5 ℃, inject 5ml anhydrous cyclohexane and 1.5g exsiccant ethyl styrene and 1.5ml n-Butyl Lithium (2.8M) solution by syringe respectively from rubber tubing, shake up, solution becomes orange, behind the stirring 30min, injects exsiccant vinyl cyanide 1.0g by syringe from rubber tubing, add the back and stir 15min, add the small amount of methanol termination reaction.Color disappears immediately.Reaction solution is dropped in the methyl alcohol of 30ml, the adularescent precipitation generates immediately, filters, and uses the methanol wash after drying, gets white α-ethyl styrene-vinyl cyanide segmented copolymer 2.4g, yield 96%.
Have in the container of stirring and bromize hydrogen gas absorption unit at 50ml, add step (1) gained multipolymer 2g, and add chlorobenzene 25ml, add the 0.2g aluminum chloride, slowly feed oxyethane 0.4g then, led in about 3 hours.The dilute hydrochloric acid hydrolysis that adds 5ml 5% in reaction mixture, behind the branch vibration layer, organic layer is used anhydrous sodium sulfate drying with after a spot of water washing three times.Dried organic phase is added 50ml have in the container of stirring and bromize hydrogen gas absorption unit, drip the 1.3g phosphorus trichloride under refluxing, 4 hours times spent are till no hydrogen chloride gas is overflowed.Reactant elder generation divides three washings with 5% sodium bicarbonate aqueous solution 20ml, and then washs with less water, and anhydrous sodium sulfate drying can obtain poly-α-ethyl (2 (4)-chloroethyl) styrene-acrylonitrile segmented copolymer 1.9g, yield 76% after steaming desolventizes.
In the 50ml there-necked flask, add above-mentioned segmented copolymer 1.5g, 22ml dioxane and 0.27g Trimethylamine 99.Controlled temperature slowly stirs and spends the night at 25 ℃.With the solid press filtration of gained, filter cake washes twice with a small amount of dioxane, and drying can get poly-α-ethyl (2 (4)-chloroethyl) the styrene-acrylonitrile TMA (TriMethylAmine) straight-chain block copolymer of 1.4g, and yield is 82%.
Embodiment 4-8
The step of embodiment 4-8 is same as routine 1-3, is not both different monomers, comonomer, tertiary amine in the employing table one, obtains corresponding alpha-methyl styrene polymer type quaternary ammonium salt static inhibitor or sterilant.
Table 2
Embodiment 9-13
The step of embodiment 9-13 is same as routine 1-3, is not both different monomers, comonomer, tertiary amine in the employing table one, obtains corresponding α-ethyl styrene polymer type antistatic agent or sterilant.
Table 3
Embodiment 14-18
The step of embodiment 14-18 is same as routine 1-3, is not both different monomers, comonomer, tertiary amine in the employing table one, obtains corresponding styrene polymer type static inhibitor or sterilant.
Table 4
Embodiment 19-23
The step of embodiment 19-23 is same as routine 1-3, is not both different monomers, comonomer, tertiary amine in the employing table one, obtains corresponding α-phenetole ethene polymers type static inhibitor or sterilant.
Table 5
Claims (5)
1, vinylbenzene or substituted phenylethylene polymer-type quaternary ammonium salt static inhibitor or sterilant is characterized in that chemical structural formula is:
Wherein X is a comonomer, be ethene, propylene, divinyl, isoprene, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid-α-hydroxyl ethyl ester, senecioate-hydroxyl ethyl ester, the vinylformic acid hydroxy butyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid-α-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, the methacrylic acid hydroxy butyl ester, MALEIC ANHYDRIDE or vinyl cyanide, comonomer X can one or more, form binary or multipolymer, the molar ratio of comonomer and vinylbenzene or substituted phenylethylene is 1: 10 to 10: 1; N is 2 to 200 integers, forms the mixture of vinylbenzene or substituted phenylethylene homopolymer or multipolymer; M is 1,2 or 3 integer, in ortho position and/or 1 to 3 replacement of contraposition formation of phenyl ring; The R substituting group is hydrogen, methyl, ethyl, chloromethyl, brooethyl, methylol, halogen, nitro, phenyl, benzyl, methoxyl group, oxyethyl group, tert.-butoxy, methylthio group, ethylmercapto group, rosickyite base, thiophenyl, to methylbenzene sulfenyl, carboxyl, methoxycarbonyl, ethoxy carbonyl, propenyloxy group carbonyl, metacryloxy carbonyl or sulfonic group; The Y negative ion is the gegenion of quaternary ammonium salt in the formula, is chlorion, bromide anion; R
1, R
2And R
3Be respectively C
1～C
24Alkyl, benzyl, tallow, h-tallow base, cocoyl, hydrogenation cocoyl, oil base, guar gum hydroxypropyl, poly-propoxy-, butter amido-ethyl, isostearoyl aminocarbonyl propyl, Viscotrol C amidopropyl, vinyl pyrrolidone-methacryloyl amido propyl group or alkyl imidazoline base, R
1, R
2And R
3Can be identical or different, eight above alkyl of carbon atom can only have one simultaneously and be present in the molecule; On the main chain of vinylbenzene or substituted phenylethylene polymer molecular chain, grafting 1-3n contains quaternary ammonium moiety, forms the mixture of molecular weight 400-200000.
2,, it is characterized in that described X is ethene, propylene, divinyl, isoprene, methyl acrylate, methyl methacrylate, butyl methacrylate or vinyl cyanide according to vinylbenzene or the substituted phenylethylene polymer-type quaternary ammonium salt static inhibitor or the sterilant of claim 1; Described R
1, R
2And R
3Be respectively methyl, ethyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isooctadecane base, eicosyl, docosyl, tetracosyl, benzyl, tallow, h-tallow base, cocoyl, hydrogenation cocoyl, oil base, guar gum hydroxypropyl, poly-propoxy-, butter amido ethyl, isostearoyl aminocarbonyl propyl, Viscotrol C amidopropyl or vinyl pyrrolidone-methacryloyl amido propyl group; Described vinylbenzene or substituted phenylethylene multipolymer are random copolymers, segmented copolymer or alternating copolymer.
3,, it is characterized in that described substituted phenylethylene is vinyl toluene, ethyl styrene, propylstyrene, isopropyl benzene ethene, 1-chloro-4-methyl-benzene, brooethyl vinylbenzene, chloro-styrene, bromstyrol, propenyloxy group carbonyl styrene or metacryloxy carbonyl styrene according to vinylbenzene or the substituted phenylethylene polymer-type quaternary ammonium salt static inhibitor or the sterilant of claim 1.
4, a kind of claim 1 or 2 or 3 vinylbenzene or the preparation method of substituted phenylethylene polymer-type quaternary ammonium salt static inhibitor or sterilant comprise the following steps:
(1) preparation of polymkeric substance
In the band stirred vessel of organic solvent is housed, in the presence of benzoyl peroxide or Diisopropyl azodicarboxylate, add vinylbenzene or substituted phenylethylene in 50-90 ℃, comonomer, reaction times 0.5-6 hour, the molar ratio of control benzoyl peroxide or Diisopropyl azodicarboxylate and vinylbenzene or substituted phenylethylene, comonomer is 0.002: 1 to 0.1: 2, and obtaining molecular weight is 400-50000, the vinylbenzene of n=2-200 or substituted phenylethylene homopolymerization or multipolymer; Perhaps by vinylbenzene or substituted phenylethylene, in the presence of organolithium, carry out anionoid polymerization with comonomer, preparation vinylbenzene or substituted phenylethylene homopolymer or multipolymer, the molar ratio that basic lithium and vinylbenzene or substituted phenylethylene, comonomer are wherein arranged is 0.0025: 1 to 0.25: 1; The mol ratio of comonomer and vinylbenzene or substituted phenylethylene is 1: 10 to 10: 1;
(2) ethoxylation and halogenation
In having the container of stirring, add step (1) gained vinylbenzene or substituted phenylethylene homopolymer or multipolymer, and the good solvent of adding vinylbenzene or substituted phenylethylene homopolymer or multipolymer, under 0-100 ℃, the Lewis acid that adds catalytic amount, feed oxyethane then, wherein the molar ratio of oxyethane and polymkeric substance is: 0.1: 1 to 3: 1; Use the dilute hydrochloric acid hydrolysate again, and wash organic layer with water, use the anhydrous magnesium sulfate drying organic layer; Filter and remove siccative, with organic phase be transferred to have stir and the container of hydrogen halide absorption unit in and add halogenating agent, wherein halogenating agent and oxyethane mol ratio are 1: 1,50 ℃ to reflux temperature, reacted 1-10 hour, the cooling, reactant successively is neutralized to neutrality with rare aqueous sodium hydroxide solution, wash with water then, anhydrous sodium sulfate drying steams the halogenide that can obtain vinylbenzene or substituted phenylethylene homopolymer or multipolymer after desolventizing;
(3) quaternized
In having the container of stirring, the halogenide that adds step (2) gained vinylbenzene or substituted phenylethylene homopolymer or multipolymer, and the halid good solvent of adding vinylbenzene or substituted phenylethylene homopolymerization or multipolymer, and corresponding tertiary amine, the amount mol ratio of halogen is 1: 1 on wherein said tertiary amine and vinylbenzene or substituted phenylethylene homopolymer or the multipolymer, in room temperature to 250 ℃ reaction after 2-48 hour, press filtration, filter cake washes twice with the mixture of a small amount of solvent and water, drying can get white vinylbenzene or substituted phenylethylene polymer-type quaternary ammonium salt static inhibitor or sterilant.
5,, it is characterized in that organic solvent is hexanaphthene or ethylene dichloride in the step (1) according to the preparation method of vinylbenzene or the substituted phenylethylene polymer-type quaternary ammonium salt static inhibitor or the sterilant of claim 4; Good solvent is chlorobenzene, oil of mirbane, ethylene dichloride or chloroform in the described step (2); Described Lewis acid is AlCl
3, ZnCl
2, FeCl
3, SnCl
4Or BF
3Described halogenating agent is PCl
3, PCl
5, SOCl
2, PBr
3Or PBr
5Good solvent is acetone, tetrahydrofuran (THF) or dioxane in the described step poly-(3); Described tertiary amine is a Trimethylamine 99, triethylamine, dimethyl amine, methyl-diethyl-amine, dimethyl benzylamine, diethyl benzylamine, 12～tetracosyl dimethylamine, 12～tetracosyl diethylamine, 12～tetracosyl methylbenzylamine, 12～tetracosyl ethyl benzyl amine, 12～tetracosyl methylethyl amine, 12～tetracosyl dimethyl hydroxyethyl amine, 12～tetracosane ylmethyl hydroxypropyl amine, alkyl ethyl-hydroxyethyl amine in 12～20,12～tetracosyl ethyl hydroxypropyl amine, the tallow dimethylamine, the tallow diethylamine, the tallow methylbenzylamine, the tallow ethyl benzyl amine, tallow methylethyl amine, tallow dimethyl hydroxyethyl amine, tallow methyl hydroxypropyl amine, tallow ethyl-hydroxyethyl amine, tallow ethyl hydroxypropyl amine, h-tallow base dimethylamine, h-tallow base diethylamine, h-tallow ylmethyl benzylamine, h-tallow base ethyl benzyl amine, h-tallow ylmethyl ethylamine, h-tallow ylmethyl ethylol amine, h-tallow ylmethyl hydroxypropyl amine, h-tallow base ethyl-hydroxyethyl amine, h-tallow base ethyl hydroxypropyl amine, the cocoyl dimethylamine, the cocoyl diethylamine, the cocoyl methylbenzylamine, the cocoyl ethyl benzyl amine, cocoyl methylethyl amine, cocoyl dimethyl hydroxyethyl amine, cocoyl methyl hydroxypropyl amine, cocoyl ethyl-hydroxyethyl amine, cocoyl ethyl hydroxypropyl amine, hydrogenation cocoyl dimethylamine, hydrogenation cocoyl diethylamine, hydrogenation cocoyl methylbenzylamine, hydrogenation cocoyl ethyl benzyl amine, hydrogenation cocoyl methylethyl amine, hydrogenation cocoyl dimethyl hydroxyethyl amine, hydrogenation cocoyl methyl hydroxypropyl amine, hydrogenation cocoyl ethyl-hydroxyethyl amine, hydrogenation cocoyl ethyl hydroxypropyl amine, the oil base dimethylamine, the oil base diethylamine, the oil base methylbenzylamine, the oil base ethyl benzyl amine, oil base methylethyl amine, oil base dimethyl hydroxyethyl amine, oil base methyl hydroxypropyl amine, oil base ethyl-hydroxyethyl amine, oil base ethyl hydroxypropyl amine, guar gum hydroxypropyl dimethylamine, guar gum hydroxypropyl diethylamine, guar gum hydroxypropylmethyl benzylamine, guar gum hydroxypropyl ethyl benzyl amine, guar gum hydroxypropylmethyl ethylamine, guar gum hydroxypropylmethyl ethylol amine, guar gum hydroxypropylmethyl hydroxypropyl amine, guar gum hydroxypropyl ethyl-hydroxyethyl amine, guar gum hydroxypropyl ethyl hydroxypropyl amine, poly-propoxy-dimethylamine, poly-propoxy-diethylamine, poly-propoxy-methylbenzylamine, poly-propoxy-ethyl benzyl amine, poly-propoxy-methylethyl amine, poly-propoxy-dimethyl hydroxyethyl amine, poly-propoxy-methyl hydroxypropyl amine, poly-propoxy-ethyl-hydroxyethyl amine, poly-propoxy-ethyl hydroxypropyl amine, butter amido-ethyl dimethylamine, butter amido-ethyl diethylamine, butter amido-ethyl methylbenzylamine, butter amido-ethyl ethyl benzyl amine, butter amido-ethyl methylethyl amine, butter amido-ethyl dimethyl hydroxyethyl amine, butter amido-ethyl methyl hydroxypropyl amine, butter amido-ethyl ethyl-hydroxyethyl amine, butter amido-ethyl ethyl hydroxypropyl amine, isostearoyl aminocarbonyl propyl dimethylamine, isostearoyl aminocarbonyl propyl diethylamine, isostearoyl aminocarbonyl propyl methylbenzylamine, isostearoyl aminocarbonyl propyl ethyl benzyl amine, isostearoyl aminocarbonyl propyl methylethyl amine, isostearoyl aminocarbonyl propyl dimethyl hydroxyethyl amine, isostearoyl aminocarbonyl propyl methyl hydroxypropyl amine, isostearoyl aminocarbonyl propyl ethyl-hydroxyethyl amine, isostearoyl aminocarbonyl propyl ethyl hydroxypropyl amine, Viscotrol C amidopropyl dimethylamine, Viscotrol C amidopropyl diethylamine, Viscotrol C amidopropyl methylbenzylamine, Viscotrol C amidopropyl ethyl benzyl amine, Viscotrol C amidopropyl methylethyl amine, Viscotrol C amidopropyl dimethyl hydroxyethyl amine, Viscotrol C amidopropyl methyl hydroxypropyl amine, Viscotrol C amidopropyl ethyl-hydroxyethyl amine, Viscotrol C amidopropyl ethyl hydroxypropyl amine, vinyl pyrrolidone-methacryloyl amido propyl group dimethylamine, vinyl pyrrolidone-methacryloyl amido propyl group diethylamine, vinyl pyrrolidone-methacryloyl amido propyl group methylbenzylamine, vinyl pyrrolidone-methacryloyl amido propyl group ethyl benzyl amine, vinyl pyrrolidone-methacryloyl amido propyl group methylethyl amine, vinyl pyrrolidone-methacryloyl amido propyl group dimethyl hydroxyethyl amine, vinyl pyrrolidone-methacryloyl amido propyl group methyl hydroxypropyl amine, vinyl pyrrolidone-methacryloyl amido propyl group ethyl-hydroxyethyl amine, vinyl pyrrolidone-methacryloyl amido propyl group ethyl hydroxypropyl amine, methyl or ethyl imidazol(e) quinoline base dimethylamine, methyl or ethyl imidazol(e) quinoline base diethylamine, methyl or ethyl imidazol(e) quinoline ylmethyl benzylamine, methyl or ethyl imidazol(e) quinoline base ethyl benzyl amine, methyl or ethyl imidazol(e) quinoline ylmethyl ethylamine, methyl or ethyl imidazol(e) quinoline ylmethyl ethylol amine, methyl or ethyl imidazol(e) quinoline ylmethyl hydroxypropyl amine, methyl or ethyl imidazol(e) quinoline base ethyl-hydroxyethyl amine, methyl or ethyl imidazol(e) quinoline base ethyl hydroxypropyl amine; Described substituted phenylethylene is vinyl toluene, ethyl styrene, propylstyrene, isopropyl benzene ethene, 1-chloro-4-methyl-benzene, brooethyl vinylbenzene, chloro-styrene, bromstyrol, propenyloxy group carbonyl styrene or metacryloxy carbonyl styrene; Described comonomer is ethene, propylene, divinyl, isoprene, methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid-α-hydroxyl ethyl ester, senecioate-hydroxyl ethyl ester, vinylformic acid hydroxy butyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid-α-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid hydroxy butyl ester, MALEIC ANHYDRIDE or vinyl cyanide; Described organolithium is lithium ethide, propyl lithium, n-Butyl Lithium, isobutyl-lithium, phenyl lithium, naphthalene lithium, the two lithiums of divinyl or the two lithiums of isoprene.
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