Embodiment
Prepare the method for laking agent of the present invention, comprise the steps:
(1) preparation of partial monosomy:
Compound (1) and compound (2) were placed reactor in 1: 1 in molar ratio,, react 3-10 hour (preferred 5-8 hour) and get compound (3) in 0 ℃~60 ℃ (preferred 5 ℃~10 ℃);
Compound (3) can make compound shown in the formula II with compound (2) by above-mentioned similar approach again;
In like manner, compound (3) makes compound shown in the formula I with compound (4) reaction.
(2) preparation of laking agent:
Be 1 by mass ratio mainly: (2~10) with compound shown in compound shown in vinylsiloxane, the formula I and the formula II: 10, under 60 ℃~80 ℃ conditions, make initiator with Potassium Persulphate, copolymer-1 obtained target compound in 0~15 hour.
The organosilicon macromolecule aldehyde-free colour stabilizer of the present invention's preparation is compared with traditional laking agent, has safer, environmental protection, makes fabric possess more firm dyefastness, is not easy jaundice simultaneously.
Laking agent of the present invention, be a kind of be main segmental macromolecular compound with quaternary ammonium salt, introduced organosilicon segment and water-soluble reaction group (as hydroxyl or/and halogen etc.) simultaneously.In the described macromolecular compound, the oxonium ion group can generate color lake (fixation) with the anionic group reaction in the dyestuff; Its organosilicon segment can improve the flexibility of fabric, and smooth property has improved fastness to wet rubbing; And hydroxyl, groups such as chloro can form crosslinking structure with the fabric fibre reaction, have improved the washing fastness of fabric, fastness to wet rubbing greatly.Therefore, not only environmental protection of laking agent of the present invention (not aldehyde-containing type compound), and have good dye fastness and dye.
The invention will be further elaborated below by embodiment, and its purpose only is better to understand content of the present invention, and unrestricted protection scope of the present invention.
Embodiment 1
Synthesizing of DMAA:
In the 100ml flask, add 45 gram dimethylamine solutions (33%), under 5 ℃ of conditions, alternately drip the propenyl chloride and the aqueous sodium hydroxide solution of same molar, react after 6 hours, product is divided into three layers of oil reservoir, water layer and solid layers, filter, get the upper strata oil reservoir behind the separatory, with obtaining faint yellow pungency liquid after the sodium hydrate solid drying.
Synthesizing of dimethyl diallyl ammonium chloride:
Add the 10ml DMAA and with the propenyl chloride of molar weight, add the 50ml acetone solvent again in the 100ml flask, carry out quaterisation under 60 ℃, react after 3-4 hour, layering appears in product, and separatory takes off a layer dimethyl diallyl ammonium chloride liquid.
Synthesizing of hexadecyldimethyl benzyl ammonium allyl ammonium chloride:
Get Virahol 100ml and place flask to make solvent, get hexadecyldimethyl benzyl ammonium tertiary amine 20ml and propenyl chloride 25ml, logical nitrogen protection, reaction is after 6-8 hour down at 60 ℃, and behind activated carbon decolorizing, the choosing steaming obtains weak yellow liquid after removing and desolvating.
Synthesizing of laking agent:
Get dimethyl diallyl ammonium chloride 10 grams, 1 gram vinyl silicone oil (molecular weight 950-1050, contents of ethylene are 5wt%) hexadecyldimethyl benzyl ammonium allyl ammonium chloride, 2 grams, Hydroxyethyl acrylate 2 grams, K
2S
2O
8Get 0.040 gram as initiator, logical nitrogen protection was reacted 10-15 hour down at 60 ℃, and obtaining thickness village liquid is laking agent, and its performance (dyefastness) sees Table 1.
Embodiment 2
Synthesizing of DMAA:
In the 100ml flask, add 45 gram dimethylamine solutions (33%), under 5 ℃ of conditions, alternately drip the propenyl chloride and the aqueous sodium hydroxide solution of same molar, react after 6 hours, product is divided into three layers of oil reservoir, water layer and solid layers, filter, get the upper strata oil reservoir behind the separatory, with obtaining faint yellow pungency liquid after the sodium hydrate solid drying.
Synthesizing of dimethyl diallyl ammonium chloride:
Add the 10ml DMAA and with the propenyl chloride of molar weight, add the 50ml acetone solvent again in the 100ml flask, carry out quaterisation under 60 ℃, react after 3-4 hour, layering appears in product, and separatory takes off a layer dimethyl diallyl ammonium chloride liquid.
Synthesizing of dimethyl-allyl benzyl ammonium chloride:
Get Benzyl Chloride 9.633g (0.0761mol) in the 50ml there-necked flask, add the 10ml dehydrated alcohol again, get 7.128g DMAA (0.0837mol), be dissolved in the 5ml dehydrated alcohol, add in the constant pressure funnel, one side mouth is loaded onto reflux condensing tube and upper end dress monochlor(in)ate calcium drying tube, live (lucifuge) reaction system with black paper bag then, 60 ℃ of temperature of reaction, DMAA solution dripped off in 8 minutes, 60 ℃ of holding temperatures continue reaction 3 hours, and decompression steams the solvent dehydrated alcohol then, use 10ml anhydrous diethyl ether washing reaction thing 3 times again, make product be solid state, normal pressure steams the small amount of residual anhydrous diethyl ether, obtains the dimethyl-allyl benzyl ammonium chloride after the vacuum-drying.
Synthesizing of laking agent:
Get dimethyl diallyl ammonium chloride 10 grams, 1 gram vinyl silicone oil (molecular weight 950-1050, contents of ethylene are 5wt%), methacrylic benzyl ammonium chloride 2 grams, Hydroxyethyl acrylate 2 grams, K
2S
2O
8Get 0.040 gram as initiator, logical nitrogen protection was reacted 10-15 hour down at 60 ℃, and obtaining thickness village liquid is laking agent, and its performance (dyefastness) sees Table 1.
Embodiment 3
Synthesizing of DMAA:
In the 100ml flask, add 45 gram dimethylamine solutions (33%), under 5 ℃ of conditions, alternately drip the propenyl chloride and the aqueous sodium hydroxide solution of same molar, react after 6 hours, product is divided into three layers of oil reservoir, water layer and solid layers, filter, get the upper strata oil reservoir behind the separatory, with obtaining faint yellow pungency liquid after the sodium hydrate solid drying.
Synthesizing of dimethyl diallyl ammonium chloride:
Add the 10ml DMAA and with the propenyl chloride of molar weight, add the 50ml acetone solvent again in the 100ml flask, carry out quaterisation under 60 ℃, react after 3-4 hour, layering appears in product, and separatory takes off a layer dimethyl diallyl ammonium chloride liquid.
Synthesizing of dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride:
In the 100ml there-necked flask, add the 9ml DMAA, add 50ml acetone and make solvent, the 9ml epoxy chloropropane is added in the dropping funnel, control reaction temperature is at 60 ℃, epoxy chloropropane dripped off in 30 minutes, after reacting 6 hours, layering appears in product, obtains lower floor's viscous liquid product with decantation.
Synthesizing of laking agent
Get dimethyl diallyl ammonium chloride 10 grams, 1 gram vinyl silicone oil (molecular weight 950-1050, contents of ethylene are 5wt%), dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride 2 grams, Hydroxyethyl acrylate 2 grams, K
2S
2O
8Get 0.040 gram as initiator, logical nitrogen protection was reacted 10-15 hour down at 60 ℃, and obtaining thickness village liquid is laking agent, and its performance (dyefastness) sees Table 1.
Embodiment 4
Synthesizing of DMAA:
In the 100ml flask, add 45 gram dimethylamine solutions (33%), under 5 ℃ of conditions, alternately drip the propenyl chloride and the aqueous sodium hydroxide solution of same molar, react after 6 hours, product is divided into three layers of oil reservoir, water layer and solid layers, filter, get the upper strata oil reservoir behind the separatory, with obtaining faint yellow pungency liquid after the sodium hydrate solid drying.
Synthesizing of dimethyl diallyl ammonium chloride
Add the 10ml DMAA and with the propenyl chloride of molar weight, add the 50ml acetone solvent again in the 100ml flask, carry out quaterisation under 60 ℃, react after 3-4 hour, layering appears in product, and separatory takes off a layer dimethyl diallyl ammonium chloride liquid.
Synthesizing of dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride
In the 100ml there-necked flask, add the 9ml DMAA, add 50ml acetone and make solvent, the 9ml epoxy chloropropane is added in the dropping funnel, control reaction temperature is at 60 ℃, epoxy chloropropane dripped off in 30 minutes, after reacting 6 hours, layering appears in product, obtains lower floor's viscous liquid product with decantation.
Synthesizing of methacrylic benzyl ammonium chloride:
Get Benzyl Chloride 9.633g (0.0761mol) in the 50ml there-necked flask, add the 10ml dehydrated alcohol again, get 7.128g DMAA (0.0837mol), be dissolved in the 5ml dehydrated alcohol, add in the constant pressure funnel, one side mouth is loaded onto reflux condensing tube and upper end dress monochlor(in)ate calcium drying tube, live (lucifuge) reaction system with black paper bag then, 60 ℃ of temperature of reaction, DMAA solution dripped off in 8 minutes, 60 ℃ of holding temperatures continue reaction 3 hours, and decompression steams the solvent dehydrated alcohol then, use 10ml anhydrous diethyl ether washing reaction thing 3 times again, make product be solid state, normal pressure steams the small amount of residual anhydrous diethyl ether, obtains the dimethyl-allyl benzyl ammonium chloride after the vacuum-drying.
Synthesizing of laking agent:
Get dimethyl diallyl ammonium chloride 10 grams, 1 gram vinyl silicone oil (molecular weight 950-1050, contents of ethylene are 5wt%), dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride 2 grams, methacrylic benzyl ammonium chloride 2 grams, K
2S
2O
8Get 0.040 gram as initiator, logical nitrogen protection was reacted 10-15 hour down at 60 ℃, and obtaining thickness village liquid is laking agent, and its performance (dyefastness) sees Table 1.
Embodiment 5
Synthesizing of DMAA:
In the 100ml flask, add 45 gram dimethylamine solutions (33%), under 5 ℃ of conditions, alternately drip the propenyl chloride and the aqueous sodium hydroxide solution of same molar, react after 6 hours, product is divided into three layers of oil reservoir, water layer and solid layers, filter, get the upper strata oil reservoir behind the separatory, with obtaining faint yellow pungency liquid after the sodium hydrate solid drying.
Synthesizing of dimethyl diallyl alkyl ammomium chloride:
Add the 10ml DMAA and with the propenyl chloride of molar weight, add the 50ml acetone solvent again in the 100ml flask, carry out quaterisation under 60 ℃, react after 3-4 hour, layering appears in product, and separatory takes off a layer dimethyl diallyl ammonium chloride liquid.
Synthesizing of dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride:
In the 100ml there-necked flask, add the 9ml DMAA, add 50ml acetone and make solvent, the 9ml epoxy chloropropane is added in the dropping funnel, control reaction temperature is at 60 ℃, epoxy chloropropane dripped off in 30 minutes, after reacting 6 hours, layering appears in product, obtains lower floor's viscous liquid product with decantation.
Synthesizing of hexadecyldimethyl benzyl ammonium allyl ammonium chloride:
Get Virahol 100ml and place flask to make solvent, get hexadecyldimethyl benzyl ammonium tertiary amine 20ml and propenyl chloride 25ml, logical nitrogen protection, reaction is after 6-8 hour down at 60 ℃, and behind activated carbon decolorizing, the choosing steaming obtains weak yellow liquid after removing and desolvating.Synthesizing of laking agent:
Get dimethyl diallyl ammonium chloride 10 grams, 1 gram vinyl silicone oil (molecular weight 950-1050, contents of ethylene are 5wt%), dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride 2 grams, hexadecyldimethyl benzyl ammonium allyl ammonium chloride 2 grams, K
2S
2O
8Get 0.040 gram as initiator, logical nitrogen protection was reacted 10-15 hour down at 60 ℃, and obtaining thickness village liquid is laking agent, and its performance (dyefastness) sees Table 1.
Embodiment 6
Synthesizing of DMAA:
In the 100ml flask, add 45 gram dimethylamine solutions (33%), under 5 ℃ of conditions, alternately drip the propenyl chloride and the aqueous sodium hydroxide solution of same molar, react after 6 hours, product is divided into three layers of oil reservoir, water layer and solid layers, filter, get the upper strata oil reservoir behind the separatory, with obtaining faint yellow pungency liquid after the sodium hydrate solid drying.
Synthesizing of dimethyl diallyl alkyl ammomium chloride
Add the 10ml DMAA and with the propenyl chloride of molar weight, add the 50ml acetone solvent again in the 100ml flask, carry out quaterisation under 60 ℃, react after 3-4 hour, layering appears in product, and separatory takes off a layer dimethyl diallyl ammonium chloride liquid.
Synthesizing of dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride:
In the 100ml there-necked flask, add the 9ml DMAA, add 50ml acetone and make solvent, the 9ml epoxy chloropropane is added in the dropping funnel, control reaction temperature is at 60 ℃, epoxy chloropropane dripped off in 30 minutes, after reacting 6 hours, layering appears in product, obtains lower floor's viscous liquid product with decantation.
Synthesizing of methacrylic benzyl ammonium chloride:
Get Benzyl Chloride 9.633g (0.0761mol) in the 50ml there-necked flask, add the 10ml dehydrated alcohol again, get 7.128g DMAA (0.0837mol), be dissolved in the 5ml dehydrated alcohol, add in the constant pressure funnel, one side mouth is loaded onto reflux condensing tube and upper end dress monochlor(in)ate calcium drying tube, live (lucifuge) reaction system with black paper bag then, 60 ℃ of temperature of reaction, DMAA solution dripped off in 8 minutes, 60 ℃ of holding temperatures continue reaction 3 hours, and decompression steams the solvent dehydrated alcohol then, use 10ml anhydrous diethyl ether washing reaction thing 3 times again, make product be solid state, normal pressure steams the small amount of residual anhydrous diethyl ether, obtains the dimethyl-allyl benzyl ammonium chloride after the vacuum-drying.
Synthesizing of laking agent:
Get dimethyl diallyl ammonium chloride 10 grams, 1 gram vinyl silicone oil (molecular weight 950-1050, contents of ethylene are 5wt%), dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride 2 grams, methacrylic benzyl ammonium chloride 2 grams, Hydroxyethyl acrylate 2 grams, K
2S
2O
8Get 0.040 gram as initiator, logical nitrogen protection was reacted 10-15 hour down at 60 ℃, and obtaining thickness village liquid is laking agent, and its performance (dyefastness) sees Table 1.
Embodiment 7
Synthesizing of methacrylic amine:
In the 100ml flask, add 45 gram dimethylamine solutions (33%), under 5 ℃ of conditions, alternately drip the propenyl chloride and the aqueous sodium hydroxide solution of same molar, react after 6 hours, product is divided into three layers of oil reservoir, water layer and solid layers, filter, get the upper strata oil reservoir behind the separatory, with obtaining faint yellow pungency liquid after the sodium hydrate solid drying.
Synthesizing of dimethyl diallyl alkyl ammomium chloride:
Add the 10ml DMAA and with the propenyl chloride of molar weight, add the 50ml acetone solvent again in the 100ml flask, carry out quaterisation under 60 ℃, react after 3-4 hour, layering appears in product, and separatory takes off a layer dimethyl diallyl ammonium chloride liquid.
Synthesizing of hexadecyldimethyl benzyl ammonium allyl ammonium chloride:
Get Virahol 100ml and place flask to make solvent, get hexadecyldimethyl benzyl ammonium tertiary amine 20ml and propenyl chloride 25ml, logical nitrogen protection, reaction is after 6-8 hour down at 60 ℃, and behind activated carbon decolorizing, the choosing steaming obtains weak yellow liquid after removing and desolvating.
Synthesizing of dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride:
In the 100ml there-necked flask, add the 9ml DMAA, add 50ml acetone and make solvent, the 9ml epoxy chloropropane is added in the dropping funnel, control reaction temperature is at 60 ℃, epoxy chloropropane dripped off in 30 minutes, after reacting 6 hours, layering appears in product, obtains lower floor's viscous liquid product with decantation.
Synthesizing of laking agent:
Get dimethyl diallyl ammonium chloride 10 grams, 1 gram vinyl silicone oil (molecular weight 950-1050, contents of ethylene are 5wt%), dimethyl-allyl (2-hydroxyl-3-chlorine) propyl ammonium chloride 2 grams, hexadecyldimethyl benzyl ammonium allyl ammonium chloride 2 grams, Hydroxyethyl acrylate 2 grams, K
2S
2O
8Get 0.040 gram as initiator, logical nitrogen protection was reacted 10-15 hour down at 60 ℃, and obtaining thickness village liquid is laking agent, and its performance (dyefastness) sees Table 1.
Table 1:
Annotate:
1. multiple, the Shi Lixin of Cui Lian. the production of color fixing agent Y and application [J]. Shenyang chemical industry .1991,2:37-39.
2. positively charged ion, Organosilicon dye fixing agent of reaction type and its preparation method (CN1583763).