CN101698655B - Method for synthesizing 2-ethoxy n-octyl thioether through three phase transfer catalysis without solvent - Google Patents
Method for synthesizing 2-ethoxy n-octyl thioether through three phase transfer catalysis without solvent Download PDFInfo
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Abstract
The invention discloses a new method for synthesizing 2-ethoxy n-octyl thioether through three phase transfer and catalysis without solvent, belonging to the technical field of fine chemicals synthetization. The method takes octyl mercaptan and 2-chlorohydrin as main raw materials, and uses organic macromolecule materials as the carrier, surface chemical modification is carried out, grafted polyethyleneglycol and quaternary ammonium salt with proper link and group structures are taken as the three phase transfer catalyst, the reaction is carried out for 6-12 hours at normal pressure and temperature of 40-90 DEG C without solvent to synthesize 2-ethoxy n-octyl thioether. Compared with the existing methods, the invention is characterized by available raw materials, low cost of production, mild reaction conditions, easy separation of the product after reaction, energy saving and consumption reducing. The three phase transfer catalyst has high activity, excellent selectivity, and good mechanical strength, and is easy to recycle from the reaction system. The invention has better industrialization application prospect.
Description
Technical field
The invention belongs to the fine chemicals synthesis technical field, relate to the compound method of organic thioether, refer more particularly to the compound method of asymmetric thioether.More detailed, the present invention relates to 2-hydroxyethyl n-octyl thioether (keeping away worm alcohol) compound method.
Background technology
Keep away worm alcohol and be a kind of novel little poison (being close to nontoxic), insect repellent efficiently, mosquito, fly, reptile, ant, bedbug etc. are had efficient repellent action, can in office that personnel concentrate, restaurant, family, garden, use.In addition, it also is a kind of nonionogenic tenside commonly used, can be used as antiwear additive and is added in the lubricating oil, and still a kind of antagonist is used for agricultural, and is slow with farm crop severe deformities and growth that relieving herbicide causes.
At present, do not see bibliographical information in China as yet about keeping away synthesizing of worm alcohol.External synthetic main method of keeping away worm alcohol has reduction reaction, substitution reaction, permutoid reaction and addition reaction method.
1 reduction reaction
(1) simple substance bromine reduction [Derzhinskii A R; Chizhov O S; Prilezhaeva EN.Functional sulfur-containing compounds.Part 4.Synt-hesis ofchloro (bromo) alkyl sulfones by oxidative halogenation of hydroxyalkylsulfides and sulfoxides using hydrogen peroxide-halogen acid mixture [J] .Izvestiya Ak ademii Nauk SSSR; Seriya; Khimich-eskaya, 1982, (5): 1116-1123.]
Derzhinskii etc. keep away worm alcohol with the preparation of simple substance bromine reduction hydroxyethyl n-octyl sulphoxide, and reaction equation is:
This method yield is lower, is merely 26%, and is raw material with the hydroxyethyl n-octyl sulphoxide, is difficult for obtaining.With the simple substance bromine reduction side reaction takes place easily, sulfoxide can be generated hydroxyethyl n-octyl sulfone by the bromine oxidation.
(2) LiAlH
4Method [Derzhinskii A R; Chizhov O S; Prilezhaeva E N.Oxidativechlorination of 2-hydroxyethyl alkyl sulfides and 2-hydroxyethyl alkylsulfoxides [J] .Organosulfur Compounds; 1977, (4): 775-778.]
A.R.Derzhinskii etc. are that reductive agent has prepared and keeps away worm alcohol with the lithium aluminum hydride, and reaction formula is following:
In the experiment to make reaction vessel, to containing C with there-necked flask
8H
17SCH
2COOC
2H
5Anhydrous ether solution in dropwise add LiAlH
4Anhydrous ether solution, controlled temperature is at 5～10 ℃, then heated and boiled 40min.Reaction mixture is used MgSO earlier
4Drying is carried out underpressure distillation then and is promptly got product.
This method reaction is simpler, easy and simple to handle, and condition is also gentle.But raw material is difficult for obtaining, severe reaction conditions, and product yield is also very low.
2 substitution reactions [Sokobwski A.Chemical structure and thermodynamics ofamphiphile solutions.1.Solubility of alkylthiooligooxyethylene glycolsin water [J] .The Journal of Physical Chemistry; 1989,93 (25): 8223-8226.]
Adam Sokolowski is a raw material with octyl mercaptan and ethylene chlorhydrin, and prepared in reaction obtains keeping away worm alcohol in sodium methoxide solution, and reaction equation is following:
Reaction is homogeneous reaction under the condition that methyl alcohol exists, and reaction raw materials also obtains easily, and product yield is higher, but carries out in the homogeneous phase for making to be reflected at, be in a large number methyl alcohol with an organic solvent, the solvent recuperation power consumption is big, product postprocessing with separate purify inconvenient.
3 permutoid reactions [Malievskii A D.Exchange reaction of oxiranes with β hydroxyalkyl sulfides; Selenides, amines, and phosph-ines [J] .RussianChemical Bulletin; 2000,49 (4): 579-587.]
This method is to be that feedstock production is kept away worm alcohol with 2-alkyl hydroxyethyl n-octyl thioether and oxyethane, and reaction equation is following:
R＝Me，Ph，CH
2OPh
The characteristics of this method are to remove to keep away worm alcohol and the generation of epoxy compounds no coupling product, and reaction is generally carried out in autoclave, is solvent with the chlorobenzene, and temperature of reaction is generally 150 ℃, no heat effect.But because this reaction is reversible reaction, so raw material reaction is incomplete, reaction belongs to high-temperature high-voltage reaction, can not satisfy the requirement of national energy-saving and emission-reduction.And the material thioether that uses also is difficult for obtaining.
4 addition reactions
(1) 1-octene method [Hiroaki K, Izumi T.Preparation of sulfides from olefinsand mercaptans [P] .JP:2002121182,2002-04-23.]
This method has been synthesized under catalyst action with 1-octene and mercaptoethanol and has been kept away worm alcohol.The reaction equation of this method is following:
The investigator has attempted three kinds of catalyzer: the hydroxide aqueous solution of triethylamine, sodium methylate and benzyl trimethyl ammonium carries out catalysis to reaction, and the result finds that the triethylamine catalytic effect is best.This method belongs to green economy type reaction, but raw material 1-octene relatively costliness be difficult to obtain, prospects for commercial application is little in China.
(2) epoxyethane method [Chlebicki J; Cichacz Z.The kinetics of oxiranereaction with alkanethiols in the presence of basic catalysts [J] .International Journal of Chemical Kinetics; 1988,20 (5): 387-395.]
Epoxyethane method is to be that raw material reacts under the sodium Metal 99.5 effect and makes product with oxyethane and octyl mercaptan.Reaction equation is following:
The advantage of this method is that raw material sources are wide, obtain easily, but this method by product is more, and yield is not high, and uses sodium Metal 99.5 danger higher.
Summary of the invention
The object of the invention is to provide a kind of raw material resources of basing on our country, Synthetic 2 under the organic solvent-free condition-hydroxyethyl n-octyl thioether, and it is low to reach production cost; Reaction conditions is gentle, and after the reaction, product separation is easy; Energy-saving and cost-reducing, catalyst activity is high, and selectivity is good; Catalyzer is easy to from the reaction system recovery and can be recycled, thereby sets up a kind of new process of realizing the Synthetic 2-hydroxyethyl n-octyl thioether of suitability for industrialized production.
For realizing the object of the invention; The present invention is a main raw material with octyl mercaptan, ethylene chlorhydrin; With organic polymer material grafting polyoxyethylene glycol or quaternary ammonium salt is the three-phase phase-transfer catalytic agent; With alkali or base brine solution is water, adopts solventless method three-phase phase-transfer catalytic Synthetic 2-hydroxyethyl n-octyl thioether.Concrete steps are following: in reaction system, add alkali or basic salt and deionized water, stirring and dissolving feeds nitrogen protection, adds organic polymer material grafting polyethyleneglycol catalyst or organic polymer material grafting quaternary ammonium salt catalyst and octyl mercaptan; Drip ethylene chlorhydrin then, organic solvent-free is under the normal pressure; 40-90 ℃, to react 6-12 hour, reaction finishes after-filtration and goes out catalyzer; The filtrating standing demix is isolated oil phase, water, and oil phase is 2-hydroxyethyl n-octyl thioether product.Catalyzer is after the extracting of apparatus,Soxhlet's organic solvent is handled, and circulation is used for building-up process.Apparatus,Soxhlet's extracting solvent for use is a chloroform, THF, and toluene, benzene, hexanaphthene, 1, the 2-ethylene dichloride, ethanol, methyl alcohol is one of in the acetone or two kinds of mixed solutions.Octyl mercaptan and ethylene chlorhydrin mol ratio are 1: 1-3, and catalyzer and octyl mercaptan weight ratio are 1: 5-50, used alkali and basic salt are sodium hydroxide, yellow soda ash, Pottasium Hydroxide or salt of wormwood, alkali or basic salt and octyl mercaptan mol ratio are 0.3-1.2: 1.
This reaction catalyst system therefor is one of following general formula compound:
Wherein, PS representes the polystyrene resins skeleton, and PVC representes the polyvinyl chloride resin skeleton; R
1, R
2C respectively does for oneself
1-C
8Straight chained alkyl or the substituted straight chained alkyl of hydroxyl; R
3Be C
1-C
22Straight chained alkyl or the substituted straight chained alkyl of hydroxyl or benzyl or phenyl; PEG representes :-(OCH
2CH
2) nOH, the average molecular mass of PEG is 200,300,400,600,800; The n=6-30 integer; X is Cl or Br.
The preferred polystyrene graft Macrogol 200 of organic polymer grafting polyethyleneglycol catalyst, 300,400 or 600; Polyvinyl chloride graft Macrogol 200,300,400 or 600.
The preferred R of organic polymer grafting quaternary ammonium salt catalyst
1, R
2C respectively does for oneself
2～C
8Straight chained alkyl or C
1～C
2The substituted straight chained alkyl of hydroxyl; R
3Be C
2～C
12Straight chained alkyl or C
1～C
2The substituted straight chained alkyl of hydroxyl or benzyl or phenyl; X is Cl or Br.More preferably polystyrene graft triethyl ammonium chloride, polystyrene graft triethyl brometo de amonio, polystyrene graft trihydroxyethyl ammonium chloride; Polystyrene graft three normal-butyl chlorination ammoniums, polystyrene graft three normal-butyl bromination ammoniums, polystyrene graft three n-octyl chlorination ammoniums; Polystyrene graft three n-octyl bromination ammoniums, polystyrene graft dimethyl n octyl group ammonium chloride, polystyrene graft dimethyl n octyl group brometo de amonio; Polystyrene graft dimethyl-dodecyl chlorination ammonium, polystyrene graft dimethyl-dodecyl bromination ammonium, polystyrene graft dimethyl benzyl ammonium chloride; Polystyrene graft dimethyl benzyl brometo de amonio, polyvinyl chloride graft triethyl ammonium chloride, polyvinyl chloride graft triethyl brometo de amonio; Polyvinyl chloride graft trihydroxyethyl ammonium chloride, polyvinyl chloride graft three normal-butyl chlorination ammoniums, polyvinyl chloride graft three normal-butyl bromination ammoniums; Polyvinyl chloride graft three n-octyl chlorination ammoniums, polyvinyl chloride graft three n-octyl bromination ammoniums, polyvinyl chloride graft dimethyl-dodecyl chlorination ammonium; Polyvinyl chloride graft dimethyl-dodecyl bromination ammonium, polyvinyl chloride graft dimethyl benzyl ammonium chloride, polyvinyl chloride graft dimethyl benzyl brometo de amonio.
With chloromethylated polystyrene-divinylbenzene resin (PS) is that example is explained above-mentioned Preparation of catalysts method.
1) preparation of PS grafting polyoxyethylene glycol phase-transfer catalyst
With 3-4g chloromethylated polystyrene-divinylbenzene resin with 20-30mL toluene or THF swelling after, put into the 100mL there-necked flask, (chlorine and polyoxyethylene glycol mol ratio are 1: 5-10) to add an amount of polyoxyethylene glycol; And 10-20mL 40% potassium hydroxide solution and 0.1-0.6g Tetrabutyl amonium bromide; Back flow reaction 8-12h, cooled and filtered is washed with 5mL Hydrogen chloride; Use distilled water wash again; Used the ethanol extracting at last 12-24 hour, vacuum-drying promptly gets PS grafted polyethyleneglycol catalyst to constant weight.
2) preparation of PS grafting quaternary ammonium salt phase transfer catalyst
Exsiccant chloromethylated polystyrene-divinylbenzene resin 5g is placed the 100mL there-necked flask, and with 20-50mL 1, the mixed solvent of 2-ethylene dichloride and 5-20mL absolute ethyl alcohol is heated to 40-60 ℃ of swelling.According to chlorine and tertiary amine mol ratio is 1: 2-8 adds tertiary amine, and suction filtration separates behind the back flow reaction 8-12h, washing with alcohol.Use apparatus,Soxhlet's with absolute ethyl alcohol extracting 12-24h.Vacuum-drying to constant weight and weighing under the room temperature promptly obtains polystyrene-divinylbenzene grafting quaternary ammonium salt.
With SE (PVC) resin is carrier, with reference to above-mentioned reaction conditions, can make SE (PVC) grafting polyoxyethylene glycol, quaternary ammonium salt catalyst.
Also can reference [Yu Shanxin, Liu Wenqi. polystyrene-supported polyoxyethylene glycol synthetic and characterize [J]. polymer journal, 1994; (3): 269-275.] reach [Ou Zhize; Xu Mancai, Yu Shanxin is prone to hypo. and polystyrene-supported quaternary ammonium salt phase-transfer catalysis specific activity is [J]. Journal of Natural Science of Hunan Normal University; 1999,22 (2): 55-58.] synthetic.
With CDCl
3Be solvent, synthetic kept away worm alcohol product carry out
1H-NMR analyzes, and on NEXUS-470 type Fourier transform infrared spectroscopy (FTIR) appearance, product is carried out infrared analysis; The synthetic product is with its content of GC-9800 gas Chromatographic Determination.
GC conditions is following:
Chromatographic column: Φ 1 μ m (I.D.) * 30m capillary column look SE-54;
Carrier gas: N
2Detector: FID; Press before the post: 0.05MPa; Vaporizing chamber: 280 ℃; Detector; 280 ℃;
Temperature programming: 200 ℃ of insulation 4min, 20 ℃/min, be warming up to 260 ℃, be cooled to 200 ℃ behind the insulation 5min.
Advantage of the present invention: 1, the octyl mercaptan of good raw material resources and ethylene chlorhydrin are arranged is raw material with domestic, and production cost is lower.2, organic solvent-free need not add harmful, deleterious solvent such as chloroform, methylene dichloride, 1,2-ethylene dichloride, toluene etc.; Reaction system is simple, adopts phase transfer of technology, reaction temperature with; Building-up process is easy, and reaction is carried out at normal temperatures and pressures, and there are obvious phase interface in reaction back oil phase and water; The nature phase-splitting can realize effective separation smoothly, and separating technology is easy.Saved the product separation costs greatly, oil phase need further not handled just can obtain the 2-hydroxyethyl n-octyl thioether of purity more than 98%, no coupling product.System of the present invention is equally applicable to add the system of organic solvent.3, the triphase-transfer catalyst of the present invention's use adopts the mode of chemically bonded to be grafted on the organic polymer material carrier; It is big to have specific surface area; Advantages such as catalytic activity is high, and the good and physical strength of selectivity is good are being reacted after simple filtering can be separated with reaction system well; It is convenient to reclaim, and after simple process, promptly can be recycled.And this catalyzer is close to nontoxic, can be used as fuel after discarding, and environment is not produced new pollution, is suitable for suitability for industrialized production.4, the catalyzer that uses of the present invention is in water oil biphase at the interface, in stirring at low speed even do not have and all can obtain 2 hydroxyethyl n-octyl thioethers under the condition of stirring, has avoided three-phase phase-transfer catalytic to need the shortcoming of high-speed stirring, has practiced thrift the energy greatly.
Embodiment
For the present invention being followed better explanation, it is following to lift embodiment:
Embodiment one
In reaction system, add yellow soda ash 4.2g (0.04mol) and deionized water, stirring and dissolving feeds nitrogen protection, adds octyl mercaptan 0.1mol and PS (PS) grafting PEG-200 catalyzer 1.6g; Drip ethylene chlorhydrin 0.1mol then, organic solvent-free, under the normal pressure, 40 ℃; Reacted 6 hours, reaction finishes after-filtration and goes out catalyzer, the filtrating standing demix; Isolate oil phase, water, oil phase carries out gas chromatographic analysis, keeps away worm alcohol yield 88.1%.
Under the above-mentioned reaction conditions, catalyzer PS (PS) grafting PEG-200 presses such scheme and reuses 6 times, keeps away worm alcohol average yield 87.7%.
Embodiment two
In reaction system, add salt of wormwood 8.3g (0.06mol) and deionized water, stirring and dissolving feeds nitrogen protection, adds octyl mercaptan 0.1mol and SE (PVC) grafting PEG-200 catalyzer 1.8g; Drip ethylene chlorhydrin 0.15mol then, organic solvent-free, under the normal pressure, 45 ℃; Reacted 7 hours, reaction finishes after-filtration and goes out catalyzer, the filtrating standing demix; Isolate oil phase, water, oil phase carries out gas chromatographic analysis, keeps away worm alcohol yield 84.8%.
Under the above-mentioned reaction conditions, catalyzer SE (PVC) grafting PEG-200 presses such scheme and reuses 5 times, keeps away worm alcohol average yield 83.9%.
Embodiment three
Experimental procedure is the same, and reaction conditions is following: octyl mercaptan 0.1mol, ethylene chlorhydrin 0.12mol; PS (PS) grafting PEG-400 2.0g, sodium hydroxide 4.8g (0.12mol), organic solvent-free; Under the normal pressure, 70 ℃ of reaction 10h filter out PS (PS) grafting PEG-400; Isolate oil phase, carry out gas chromatographic analysis, keep away worm alcohol yield 96.8%.
Under the above-mentioned reaction conditions, catalyzer PS (PS) grafting PEG-400 presses such scheme and reuses 6 times, keeps away worm alcohol average yield 96.3%.
Embodiment four
Experimental procedure is the same, and reaction conditions is following: octyl mercaptan 0.1mol, ethylene chlorhydrin 0.11mol; PS (PS) grafting PEG-600 2.4g, Pottasium Hydroxide 5.6g (0.1mol), organic solvent-free; Under the normal pressure, 80 ℃ of reaction 10h filter out PS (PS) grafting PEG-600; Isolate oil phase, carry out gas chromatographic analysis, keep away worm alcohol yield 95.6%.
Under the above-mentioned reaction conditions, catalyzer PS (PS) grafting PEG-600 presses such scheme and reuses 5 times, keeps away worm alcohol average yield 95%.
Embodiment five
Experimental procedure is the same, and reaction conditions is following: octyl mercaptan 0.1mol, ethylene chlorhydrin 0.3mol; PS (PS) grafting three n-octyl chlorination ammonium 1.4g, Pottasium Hydroxide 6.7g (0.12mol), organic solvent-free; Under the normal pressure, 50 ℃ of reaction 12h filter out PS (PS) grafting three n-octyl chlorination ammoniums; Isolate oil phase, carry out gas chromatographic analysis, keep away worm alcohol yield 89.4%.
Under the above-mentioned reaction conditions, catalyzer PS (PS) grafting three n-octyl chlorination ammoniums are pressed such scheme and are reused 5 times, keep away worm alcohol average yield 88.6%.
Embodiment six
Experimental procedure is the same, and reaction conditions is following: octyl mercaptan 0.1mol, ethylene chlorhydrin 0.11mol; PS (PS) grafting dimethyl-dodecyl chlorination ammonium 1.8g, salt of wormwood 4.1g (0.03mol), organic solvent-free; Under the normal pressure, 90 ℃ of reaction 12h filter out PS (PS) grafting dimethyl-dodecyl bromination ammonium; Isolate oil phase, carry out gas chromatographic analysis, keep away worm alcohol yield 80.3%.
Under the above-mentioned reaction conditions, catalyzer PS (PS) grafting dimethyl-dodecyl bromination ammonium is pressed such scheme and is reused 4 times, keeps away worm alcohol average yield 79.6%.
Embodiment seven
Experimental procedure is the same, and reaction conditions is following: octyl mercaptan 0.1mol, ethylene chlorhydrin 0.12mol; PS (PS) grafting trihydroxyethyl ammonium chloride 2.0g, sodium hydroxide 4.8g (0.12mol), organic solvent-free; Under the normal pressure, 70 ℃ of reaction 12h filter out PS (PS) grafting trihydroxyethyl ammonium chloride; Isolate oil phase, carry out gas chromatographic analysis, keep away worm alcohol yield 91.5%.
Under the above-mentioned reaction conditions, catalyzer PS (PS) grafting trihydroxyethyl ammonium chloride is pressed such scheme and is reused 5 times, keeps away worm alcohol average yield 90.2%.
Embodiment eight
Octyl mercaptan 0.1mol, ethylene chlorhydrin 0.3mol, SE (PVC) grafting dimethyl benzyl brometo de amonio 3.0g; Yellow soda ash 5.3g (0.05mol), organic solvent-free is under the normal pressure; 60 ℃ of reaction 10h filter out PS (PS) grafting dimethyl benzyl, isolate oil phase; Carry out gas chromatographic analysis, keep away worm alcohol yield 68.5%.
Under the above-mentioned reaction conditions, catalyzer SE (PVC) grafting dimethyl benzyl brometo de amonio is pressed such scheme and is reused 3 times, keeps away worm alcohol average yield 67.2%.
Claims (5)
1. organic solvent-free method three-phase phase-transfer catalytic Synthetic 2-hydroxyethyl n-octyl thioether method is characterized in that, realizes through following steps: in reaction system, add alkali or basic salt and deionized water; Stirring and dissolving feeds nitrogen protection, adds organic polymer material grafting polyethyleneglycol catalyst or organic polymer material grafting quaternary ammonium salt catalyst and octyl mercaptan; Drip ethylene chlorhydrin then, organic solvent-free is under the normal pressure; 40-90 ℃, to react 6-12 hour, reaction finishes the after-filtration catalyzer; The filtrating standing demix is isolated oil phase, water, and oil phase is 2-hydroxyethyl n-octyl thioether product; Octyl mercaptan and ethylene chlorhydrin mol ratio are 1: 1-3; Catalyzer and octyl mercaptan weight ratio are 1: 5-50; Alkali or basic salt and octyl mercaptan mol ratio are 0.3-1.2: 1; Organic polymer grafting polyoxyethylene glycol or quaternary ammonium salt catalyst have one of following general formula:
Wherein, PS representes the polystyrene resins skeleton, and PVC representes the polyvinyl chloride resin skeleton; PEG representes :-(OCH
2CH
2) nOH;
R
1, R
2C respectively does for oneself
1-C
8Straight chained alkyl or C
1～C
2The substituted straight chained alkyl of hydroxyl;
R
3Be C
1-C
22Straight chained alkyl or C
1～C
2Substituted straight chained alkyl of hydroxyl or benzyl;
X is Cl or Br;
The average molecular mass of PEG is 200,300,400,600,800; The n=6-30 integer.
2. Synthetic 2 according to claim 1-hydroxyethyl n-octyl thioether method is characterized in that used alkali or basic salt are sodium hydroxide, Pottasium Hydroxide, yellow soda ash or salt of wormwood.
3. Synthetic 2 according to claim 1-hydroxyethyl n-octyl thioether method is characterized in that organic polymer grafting polyethyleneglycol catalyst is a polystyrene graft Macrogol 200,300,400 or 600; Polyvinyl chloride graft Macrogol 200,300,400 or 600.
4. Synthetic 2 according to claim 1-hydroxyethyl n-octyl thioether method is characterized in that organic polymer grafting quaternary ammonium salt catalyst is R
1, R
2C respectively does for oneself
2～C
8Straight chained alkyl or C
1～C
2The substituted straight chained alkyl of hydroxyl; R
3Be C
2～C
12Straight chained alkyl or C
1～C
2Substituted straight chained alkyl of hydroxyl or benzyl; X is Cl or Br.
5. Synthetic 2 according to claim 1-hydroxyethyl n-octyl thioether method is characterized in that organic polymer grafting quaternary ammonium salt catalyst is the polystyrene graft triethyl ammonium chloride; Polystyrene graft triethyl brometo de amonio, polystyrene graft trihydroxyethyl ammonium chloride, polystyrene graft three normal-butyl chlorination ammoniums; Polystyrene graft three normal-butyl bromination ammoniums, polystyrene graft three n-octyl chlorination ammoniums, polystyrene graft three n-octyl bromination ammoniums; Polystyrene graft dimethyl n octyl group ammonium chloride, polystyrene graft dimethyl n octyl group brometo de amonio, polystyrene graft dimethyl-dodecyl chlorination ammonium; Polystyrene graft dimethyl-dodecyl bromination ammonium, polystyrene graft dimethyl benzyl ammonium chloride, polystyrene graft dimethyl benzyl brometo de amonio; The polyvinyl chloride graft triethyl ammonium chloride, polyvinyl chloride graft triethyl brometo de amonio, polyvinyl chloride graft trihydroxyethyl ammonium chloride; Polyvinyl chloride graft three normal-butyl chlorination ammoniums, polyvinyl chloride graft three normal-butyl bromination ammoniums, polyvinyl chloride graft three n-octyl chlorination ammoniums; Polyvinyl chloride graft three n-octyl bromination ammoniums, polyvinyl chloride graft dimethyl-dodecyl chlorination ammonium, polyvinyl chloride graft dimethyl-dodecyl bromination ammonium; The polyvinyl chloride graft dimethyl benzyl ammonium chloride, polyvinyl chloride graft dimethyl benzyl brometo de amonio.
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