CN105622945A - Darkening finishing agent and preparation method thereof - Google Patents

Darkening finishing agent and preparation method thereof Download PDF

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Publication number
CN105622945A
CN105622945A CN201610193241.1A CN201610193241A CN105622945A CN 105622945 A CN105622945 A CN 105622945A CN 201610193241 A CN201610193241 A CN 201610193241A CN 105622945 A CN105622945 A CN 105622945A
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fluorine
silicon oil
preparation
organic silicon
containing organic
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CN105622945B (en
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任一波
周文
张萍
顾永欢
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Pulcra Specialty Chemicals Shanghai Co Ltd
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Pulcra Specialty Chemicals Shanghai Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention relates to a preparation method of a darkening finishing agent. The preparation method comprises the following steps: (1) taking an octamethylcyclotetrasiloxane lineament, a 1,3,5-tris(3,3,3-trifluoropropyl)methylcyclotrisiloxane lineament, an ammonia coupling agent and an end capping agent as raw materials, and under the action of a strong basic catalyst, performing polymerization by bulk polymerization ring-opening reaction to obtain fluorine-containing amino silicon oil; (2) adding dimethylaminoethyl methacrylate into the fluorine-containing amino silicon oil to enable Machel addition reaction so as to obtain modified fluorine-containing amino silicon oil; (3) adding haloalkane into the modified fluorine-containing amino silicon oil to enable quaternization reaction so as to obtain quaternized fluorine-containing amino silicon oil; (4) performing water emulsification on quaternized fluorine-containing amino silicon oil to serve as the darkening finishing agent. The preparation method of the darkening finishing agent is environmentally friendly and free of pollution in technological process, the prepared quaternized fluorine-containing amino silicon oil has a very good darkening effect on textile fabrics, and both the styles and the hand feelings of the textile fabrics can be better maintained.

Description

The dark finishing composition of a kind of increasing and its preparation method
Technical field
The present invention relates to textile technology field, particularly relate to the dark finishing composition of a kind of increasing and its preparation method.
Background technology
In textile industry, some textiles needs to deepen its color, especially dark polyester piece good. The method making the color and luster of fabric deepen under the prerequisite not increasing dye dosage is more and more subject to people's attention, and the method is possible not only to obtain deep-colour fabric, more can save dyestuff, reduce production cost, reduces coloring matter content in dyeing waste water simultaneously.
Generally, under the prerequisite not increasing dye dosage, fabric increases dark method and can conclude as three major types: fiber is carried out physics and/or chemical treatment by (1), make textile surface coarseization, reduce the surface reflection to light, increase the absorption to dyestuff, it is to increase the Apparent Depth of DYED FABRICS and dyeing consumption; (2) setting about from improving the dye uptake of dyestuff on fabric, obtain deep-colour fabric, it comprises graft modification arrangement, resination and use short dye auxiliary agent etc.; (3) the DYED FABRICS hyperchromicity agent that normal dyeing obtains carries out aftertreatment, reduces DYED FABRICS surface and the specific refractory power of incident light obtains dark effect.
Wherein, increase dark finishing composition and the deep dyeing of yarn fabric can be had much relations with the refractive index of hyperchromicity agent. Fluorine resin is less due to specific refractory power, has and well increases dark effect, but, there is the problem that the feel of yarn fabric is unexcellent.
Summary of the invention
Based on this, it is necessary to increase, for how to obtain, the dark finishing composition problem of increasing that dark effect is better and yarn fabric feel is higher, it is provided that the dark finishing composition of a kind of increasing and its preparation method.
Increase a preparation method for dark finishing composition, comprise step:
1) by the aqueous solution of strong alkali catalyst, octamethylcyclotetrasiloxane linear body, trifluoro propyl methyl cyclotrisiloxane linear body, ammonia type coupling agent and end-capping reagent mixing, stir after evenly, lead to into nitrogen, at 180-200 rev/min of stirring velocity, 100-110 DEG C of temperature, react 4-8 hour, obtaining fluorine-containing amido silicon oil, wherein, the weight percentage of above-mentioned raw materials is:
2) by described fluorine-containing amido silicon oil, the dimethylaminoethyl methacrylate of dissolve with ethanol mixes with adopting in advance, stir after evenly, at 180-200 rev/min of stirring velocity, 20-30 DEG C of temperature, react 12-20 hour, obtain the fluorine-containing amido silicon oil of modification, wherein, the mol ratio of the primary amino in described fluorine-containing amido silicon oil and described dimethylaminoethyl methacrylate is 1:1-1:1.15;
3) under 55-75 DEG C of temperature, 180-200 rev/min of stirring velocity, haloalkane drips while stirring and adds described step 2) in the fluorine-containing amido silicon oil of modification, and react 3-6 hour, then, continue to heat up, at 180-200 rev/min of stirring velocity, 75-80 DEG C of temperature, continue reaction 1-2 hour, obtaining season ammonium fluorine-containing organic silicon oil, wherein, the mol ratio of the tertiary amine groups in the fluorine-containing amido silicon oil of described haloalkane and described modification is 1:0.8-1:1.2;
4) at 85 DEG C of temperature, by described step 3) in obtain season ammonium fluorine-containing organic silicon oil PH value be adjusted to 7, again the emulsifying agent being dissolved in advance in 20 grams of deionized waters is added to while stirring in described season ammonium fluorine-containing organic silicon oil, react 1 hour under 900-1200 rev/min of stirring velocity, obtain the season ammonium fluorine-containing organic silicon oil of emulsification, wherein, the quality of described emulsifying agent is the 0.1%-2% of quality of described season ammonium fluorine-containing organic silicon oil.
Wherein in an embodiment, in described step 1) in described ammonia type coupling agent be at least one in N-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, ��-aminopropyl methyl dimethoxysilane.
Wherein in an embodiment, in described step 1) in described end-capping reagent be hexamethyldisiloxane or pentamethyl disiloxane.
Wherein in an embodiment, described step 1) in described octamethylcyclotetrasiloxane linear body obtain in the following manner: octamethylcyclotetrasiloxane and potassium hydroxide are mixed, stir after evenly, lead to into nitrogen, at 200-400 rev/min of stirring velocity, 140-150 DEG C of temperature, react 0.5-3 hour, obtain described octamethylcyclotetrasiloxane linear body, wherein, the quality of described potassium hydroxide is the 0.1%-0.5% of the quality of described octamethylcyclotetrasiloxane.
Wherein in an embodiment, in described step 1) in described trifluoro propyl methyl cyclotrisiloxane linear body obtain in the following manner: trifluoro propyl methyl cyclotrisiloxane and Tetramethylammonium hydroxide are mixed, stir after evenly, lead to into nitrogen, at 200-400 rev/min of stirring velocity, 150-160 DEG C of temperature, react 1-5 hour, obtain described trifluoro propyl methyl cyclotrisiloxane linear body, wherein, the quality of described Tetramethylammonium hydroxide is the 0.3%-1% of the quality of described trifluoro propyl methyl cyclotrisiloxane.
Wherein in an embodiment, in described step 3) in the general formula of described haloalkane be: CH3(CH2)n-X, n are integer, and n is more than or equal to 0, and to be less than or equal to 8, X be halogen atom.
Wherein in an embodiment, in described step 4) in, by adding acetic acid, by described step 3) in obtain season ammonium fluorine-containing organic silicon oil PH value be adjusted to 7.
Wherein in an embodiment, in described step 4) in described emulsifying agent be fluorine-containing emulsifier.
Wherein in an embodiment, described fluorine-containing emulsifier is at least one in fluorine ether, oxyethyl group class non-ionic type fluorocarbon surfactant and perfluoro capryl Tetrumethylammonium Iodide compound.
A kind of increasing dark finishing composition, the dark finishing composition of described increasing is season ammonium fluorine-containing organic silicon oil, described season the structural formula of ammonium fluorine-containing organic silicon oil be:
In described structural formula, x, y, z is positive integer; The general formula of R is CH3(CH2) n, wherein, n is integer, and n is more than or equal to 0, and to be less than or equal to 8, X be halogen atom.
The dark finishing composition of above-mentioned increasing and its preparation method, taking octamethylcyclotetrasiloxane linear body, trifluoro propyl methyl cyclotrisiloxane linear body, ammonia type coupling agent and end-capping reagent as raw material, occur mass polymerization ring-opening reaction to be polymerized under the effect of strong alkali catalyst, obtain fluorine-containing amido silicon oil; In fluorine-containing amido silicon oil, add dimethylaminoethyl methacrylate again, occur to step gram addition reaction, obtain the fluorine-containing amido silicon oil of modification; Then, add haloalkane, carry out quaterisation, obtain season ammonium fluorine-containing organic silicon oil; Finally season ammonium fluorine-containing organic silicon oil is carried out emulsifying water, season ammonium fluorine-containing organic silicon oil conduct after emulsifying water increases dark finishing composition, season ammonium fluorine-containing organic silicon oil has lower refractive index containing fluorine, thus have and preferably increase dark effect, not only due to its containing but also quaternary ammonium salt ion, thus positively charged, group that can be electronegative with fiber surface is combined, it is to increase the feel of yarn fabric.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preparation method increasing dark finishing composition of an embodiment.
Embodiment
As shown in Figure 1, the preparation method increasing dark finishing composition of an embodiment, comprises step:
S1: add octamethylcyclotetrasiloxane linear body, trifluoro propyl methyl cyclotrisiloxane linear body, ammonia type coupling agent and end-capping reagent in the first reactor, occur mass polymerization ring-opening reaction to obtain fluorine-containing amido silicon oil under strong alkali catalyst.
Specifically, the first reactor is four mouthfuls of flasks, and four mouthfuls of flasks are equipped with agitator, reflux condensing tube and thermometer. In advance strong alkali catalyst is dissolved in deionized water, the strong alkali catalyst aqueous solution is joined in four mouthfuls of flasks, then, four mouthfuls of flasks add octamethylcyclotetrasiloxane linear body, trifluoro propyl methyl cyclotrisiloxane linear body, ammonia type coupling agent and end-capping reagent, by even for all raw material stirring in four mouthfuls of flasks.
Four mouthfuls of flasks lead to into nitrogen, at 180-200 rev/min of stirring velocity, 100-110 DEG C of temperature, octamethylcyclotetrasiloxane linear body, trifluoro propyl methyl cyclotrisiloxane linear body, ammonia type coupling agent and end-capping reagent react 4-8 hour under strong alkali catalyst effect. Then, it is cooled to normal temperature, obtains fluorine-containing amido silicon oil. In the present embodiment, strong alkali catalyst is potassium hydroxide or Tetramethylammonium hydroxide.
Strong alkali catalyst dissolves in deionized water, thus octamethylcyclotetrasiloxane linear body, trifluoro propyl methyl cyclotrisiloxane linear body and ammonia type coupling agent are under the effect of hydroxide radical, anionoid polymerization occurs, obtains fluorine-containing amido silicon oil. Owing to temperature of reaction is 100-110 DEG C, therefore, in strong alkali catalyst, the deionized water in the aqueous solution can volatilize after the completion of reaction.
Wherein, the weight percentage (%) of above-mentioned raw materials is:
Each composition weight percentage composition sum is 100% above.
In advance, strong alkali catalyst is dissolved in deionized water, obtain strong alkali catalyst water-soluble, wherein, the quality of deionized water is the 25-35% of the total mass of above-mentioned octamethylcyclotetrasiloxane linear body, trifluoro propyl methyl cyclotrisiloxane linear body, ammonia type coupling agent and strong alkali catalyst.
Wherein, in the present embodiment, ammonia type coupling agent is at least one in N-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, ��-aminopropyl methyl dimethoxysilane. Preferably, ammonia type coupling agent is N-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane.
End-capping reagent is hexamethyldisiloxane or pentamethyl disiloxane. Preferably, end-capping reagent is hexamethyldisiloxane.
In the present embodiment, octamethylcyclotetrasiloxane linear body and trifluoro propyl methyl cyclotrisiloxane linear body are obtained by mass polymerization respectively in advance. Octamethylcyclotetrasiloxane linear body obtains in the following manner: add octamethylcyclotetrasiloxane and potassium hydroxide being equipped with in four mouthfuls of flasks of agitator, reflux condensing tube and thermometer, stir after evenly, lead to into nitrogen, at 200-400 rev/min of stirring velocity, 140-150 DEG C of temperature, react 0.5-3 hour, obtaining described octamethylcyclotetrasiloxane linear body, wherein, the quality of described potassium hydroxide is the 0.1%-0.5% of the quality of described octamethylcyclotetrasiloxane.
Trifluoro propyl methyl cyclotrisiloxane linear body obtains in the following manner: be equipped with in four mouthfuls of flasks of agitator, reflux condensing tube and thermometer to add trifluoro propyl methyl cyclotrisiloxane and Tetramethylammonium hydroxide, stir after evenly, lead to into nitrogen, at 200-400 rev/min of stirring velocity, 150-160 DEG C of temperature, react 1-5 hour, obtain described trifluoro propyl methyl cyclotrisiloxane linear body, wherein, the quality of described Tetramethylammonium hydroxide is the 0.3%-1% of the quality of described trifluoro propyl methyl cyclotrisiloxane.
S2: add the dimethylaminoethyl methacrylate adopting dissolve with ethanol in advance in the first reactor, occurs to step gram addition reaction, obtains the fluorine-containing amido silicon oil of modification.
Specifically, dimethylaminoethyl methacrylate is dissolved in ethanol so that dimethylaminoethyl methacrylate dissolves completely. Then, added in four in step S1 mouthful flask, dimethylaminoethyl methacrylate and fluorine-containing amido silicon oil are stirred evenly. Stir after evenly, at 180-200 rev/min of stirring velocity, 20-30 DEG C of temperature, react 12-20 hour, obtain the fluorine-containing amido silicon oil of modification. Wherein, the mol ratio of the primary amino in fluorine-containing amido silicon oil and described dimethylaminoethyl methacrylate is 1:1-1:1.15.
By adding dimethylaminoethyl methacrylate, the double bond in dimethylaminoethyl methacrylate and the primary amino in fluorine-containing amido silicon oil occur to step gram addition reaction, thus introduce dimethylamino, are convenient to follow-up season ammonium.
S3: add haloalkane in the 2nd reactor, drips the fluorine-containing amido silicon oil adding modification while stirring, obtains season ammonium fluorine-containing organic silicon oil.
Specifically, 2nd reactor is four mouthfuls of flasks, by on these four mouthfuls of flasks, thermometer, reflux condensing tube and agitator are housed, four mouthfuls of flasks are placed in electric mantle, it is heated to 55-75 DEG C, and under 180-200 rev/min of stirring velocity, drips the fluorine-containing amido silicon oil adding the modification obtained in step S2 while stirring, after being added dropwise to complete, react 3-6 hour.
Then, continue to heat up so that temperature of reaction reaches 75-80 DEG C, under 180-200 rev/min of stirring velocity, continue reaction 1-2 hour. Season ammonium fluorine-containing organic silicon oil is obtained after cooling. Wherein, the mol ratio of the tertiary amine groups in the fluorine-containing amido silicon oil of haloalkane and modification is 1:0.8-1:1.2. Tertiary amine groups in the fluorine-containing amido silicon oil of haloalkane and modification is reacted, and obtains season ammonium fluorine-containing organic silicon oil. Wherein, the structural formula of season ammonium fluorine-containing organic silicon oil is:
In formula, x, y, z is positive integer; The general formula of R is CH3(CH2) n, wherein, n is integer, and n is more than or equal to 0, and to be less than or equal to 8, X be halogen atom.
In the present embodiment, the general formula of haloalkane is: CH3(CH2)n-X, n are integer, and n is more than or equal to 0, and to be less than or equal to 8, X be halogen atom.
Season ammonium fluorine-containing organic silicon oil containing quaternary ammonium salt ion so that its positively charged, group that can be electronegative with fiber surface is combined, it is to increase with fabric bonding force.
S4: season ammonium fluorine-containing organic silicon oil is carried out emulsifying water.
Specifically, at bath temperature 85 DEG C, in the 2nd reactor, add acid, regulating step S3 obtains season ammonium fluorine-containing organic silicon oil PH value to 7. In the present embodiment, the acid adopted is acetic acid. It should be noted that, acid can also be formic acid etc. In addition, it is also possible to adopt the mode of oil bath.
Then, the emulsifying agent being dissolved in advance in 20 grams of deionized waters is added to while stirring in season ammonium fluorine-containing organic silicon oil, reacts 1 hour under 900-1200 rev/min of stirring velocity, obtain the season ammonium fluorine-containing organic silicon oil of emulsification. Wherein, the quality of emulsifying agent is the 0.1%-2% of quality of season ammonium fluorine-containing organic silicon oil.
In the present embodiment, emulsifying agent is fluorine-containing emulsifier. Preferably, fluorine-containing emulsifier is at least one in fluorine ether, oxyethyl group class non-ionic type fluorocarbon surfactant and perfluoro capryl Tetrumethylammonium Iodide compound.
Due in season ammonium fluorine-containing organic silicon oil containing quaternary ammonium salt ion, thus after adding fluorine-containing emulsifier, high speed machine very easily obtains stable emulsion after stirring, and the emulsion particle diameter obtained is little, stable, and there will not be floating oil phenomenon.
The dark finishing composition of the increasing of one embodiment, the dark finishing composition of this increasing is season ammonium fluorine-containing organic silicon oil, and its structural formula is:
In formula, x, y, z is positive integer; The general formula of R is CH3(CH2) n, wherein, n is integer, and n is more than or equal to 0, and to be less than or equal to 8, X be halogen atom.
The dark finishing composition of above-mentioned increasing and its preparation method, adopt alkali catalyst catalysis octamethylcyclotetrasiloxane and trifluoro propyl methyl cyclotrisiloxane open loop, obtain octamethylcyclotetrasiloxane linear body and trifluoro propyl methyl cyclotrisiloxane linear body. Taking octamethylcyclotetrasiloxane linear body and trifluoro propyl methyl cyclotrisiloxane linear body as raw material, with ammonia type silane coupling agent copolymerization, obtain fluorine-containing amido silicon oil, utilize the primary amine in fluorine-containing amido silicon oil, occur to step gram addition reaction with dimethylaminoethyl methacrylate, obtain the fluorine-containing amido silicon oil of modification, again the fluorine-containing amido silicon oil of modification is carried out season ammonium, with emulsifying water after season ammonium, obtained increase dark finishing composition, this preparation process environmental protection, pollution-free.
In addition, it is easy to use that the season ammonium fluorine-containing organic silicon oil obtained by aforesaid method increases dark finishing composition, both can be used alone, it is possible to use composite with other amino silicon oil emulsion, and the increasing as textiles arranges deeply, is particularly suited for the dark finishing composition of increasing of polyester piece good. For the dark polyester piece good that demand in existing market is big, especially the polyester piece good of black, increases dark successful, and after arranging, the feel of textiles and style not only do not change, but also is improved.
Embodiment 1
Being joined by 50g octamethylcyclotetrasiloxane in four mouthfuls of flasks, add 0.3g potassium hydroxide, logical nitrogen, stirs evenly, at 145 DEG C of temperature, reacts 1 hour, obtained octamethylcyclotetrasiloxane linear body;
Adding 50g trifluoro propyl methyl cyclotrisiloxane in another four mouthfuls of flasks, add 0.6g Tetramethylammonium hydroxide simultaneously, logical nitrogen, stirs evenly, at 155 DEG C of temperature, reacts 2 hours, obtained trifluoro propyl methyl cyclotrisiloxane linear body;
First 0.4g Tetramethylammonium hydroxide is dissolved in 32g deionized water, then, with 39.54g octamethylcyclotetrasiloxane linear body, 20g trifluoro propyl methyl cyclotrisiloxane linear body, 8gN-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, 0.6g end-capping reagent hexamethyldisiloxane joins together and agitator is housed, in four mouthfuls of flasks of reflux condensing tube and thermometer, it is uniformly mixed, lead to into nitrogen, then 100 DEG C it are warming up to, 200 revs/min of stirring velocitys, react 6 hours at 100 DEG C of temperature, fluorine-containing amido silicon oil is obtained after cooling, this fluorine-containing amido silicon oil is even translucent thick liquid,
By above-mentioned obtained fluorine-containing amido silicon oil, add with the dimethylaminoethyl methacrylate of dissolve with ethanol, after being uniformly mixed, it is warming up to 25 DEG C, react 15 hours at 200 revs/min of stirring velocitys, 25 DEG C of temperature, obtaining the fluorine-containing amido silicon oil of modification, wherein, the primary amine of fluorine-containing amido silicon oil and the mol ratio of dimethylaminoethyl methacrylate are 1:1;
Another four mouthfuls of flasks add methyl chloride, it is warmed up to 65 DEG C, the fluorine-containing amido silicon oil adding above-mentioned modification is dripped while stirring under 200 revs/min of stirring velocitys, react after 5 hours, it is warmed up to 85 DEG C again, under same stirring velocity, continues reaction 1.5 hours, obtain the season fluorine-containing amido silicon oil of ammoniumization, wherein, in methyl chloride used and modified fluoride-containing amido silicon oil, the mol ratio of tertiary amine is 1:1;
At bath temperature 85 DEG C, drip and add acetic acid, by above-mentioned obtained season, the pH value of ammonium fluorine-containing organic silicon oil is adjusted to neutrality, then, is dissolved in 20 grams of deionized waters by emulsifying agent perfluoro capryl Tetrumethylammonium Iodide compound, slowly join in season ammonium fluorine-containing organic silicon oil while stirring, after adding, stir 1 hour under 1000 revs/min of stirring velocitys, obtain the homogeneous latex emulsion of season ammonium fluorine-containing organic silicon oil, wherein, the consumption of perfluoro capryl Tetrumethylammonium Iodide compound be season ammonium fluorine-containing organic silicon oil quality 0.5%.
Embodiment 2
Being joined by 50g octamethylcyclotetrasiloxane in four mouthfuls of flasks, add 0.3g potassium hydroxide, logical nitrogen, stirs evenly, at 145 DEG C of temperature, reacts 1 hour, obtained octamethylcyclotetrasiloxane linear body;
Adding 50g trifluoro propyl methyl cyclotrisiloxane in another four mouthfuls of flasks, add 0.6g Tetramethylammonium hydroxide simultaneously, logical nitrogen, stirs evenly, at 155 DEG C of temperature, reacts 2 hours, obtained trifluoro propyl methyl cyclotrisiloxane linear body;
First 0.4g Tetramethylammonium hydroxide is dissolved in 32g deionized water, then, with 20g octamethylcyclotetrasiloxane linear body, 30g trifluoro propyl methyl cyclotrisiloxane linear body, 8gN-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, 0.6g end-capping reagent hexamethyldisiloxane joins together and agitator is housed, in four mouthfuls of flasks of reflux condensing tube and thermometer, it is uniformly mixed, lead to into nitrogen, then 100 DEG C it are warming up to, 200 revs/min of stirring velocitys, react 6 hours at 100 DEG C of temperature, fluorine-containing amido silicon oil is obtained after cooling, this fluorine-containing amido silicon oil is even translucent thick liquid,
By above-mentioned obtained fluorine-containing amido silicon oil, add with the dimethylaminoethyl methacrylate of dissolve with ethanol, after being uniformly mixed, it is warming up to 25 DEG C, react 15 hours at 200 revs/min of stirring velocitys, 25 DEG C of temperature, obtaining the fluorine-containing amido silicon oil of modification, wherein, the primary amine of fluorine-containing amido silicon oil and the mol ratio of dimethylaminoethyl methacrylate are 1:1;
Another four mouthfuls of flasks add methyl chloride, it is warmed up to 65 DEG C, the fluorine-containing amido silicon oil adding above-mentioned modification is dripped while stirring under 200 revs/min of stirring velocitys, react after 5 hours, it is warmed up to 85 DEG C again, under same stirring velocity, continues reaction 1.5 hours, obtain the season fluorine-containing amido silicon oil of ammoniumization, wherein, in methyl chloride used and modified fluoride-containing amido silicon oil, the mol ratio of tertiary amine is 1:1;
At bath temperature 85 DEG C, drip and add acetic acid, by above-mentioned obtained season, the pH value of ammonium fluorine-containing organic silicon oil is adjusted to neutrality, then, is dissolved in 20 grams of deionized waters by emulsifying agent perfluoro capryl Tetrumethylammonium Iodide compound, slowly join in season ammonium fluorine-containing organic silicon oil while stirring, after adding, stir 1 hour under 1000 revs/min of stirring velocitys, obtain the homogeneous latex emulsion of season ammonium fluorine-containing organic silicon oil, wherein, the consumption of perfluoro capryl Tetrumethylammonium Iodide compound be season ammonium fluorine-containing organic silicon oil quality 0.5%.
Embodiment 3
Adding 50g trifluoro propyl methyl cyclotrisiloxane in four mouthfuls of flasks, add 0.6g Tetramethylammonium hydroxide simultaneously, logical nitrogen, stirs evenly, at 155 DEG C of temperature, reacts 2 hours, obtained trifluoro propyl methyl cyclotrisiloxane linear body;
First 0.4g Tetramethylammonium hydroxide is dissolved in 32g deionized water, then, with 59.34g trifluoro propyl methyl cyclotrisiloxane linear body, 8gN-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, 0.6g end-capping reagent hexamethyldisiloxane joins together and agitator is housed, in four mouthfuls of flasks of reflux condensing tube and thermometer, it is uniformly mixed, lead to into nitrogen, then 100 DEG C it are warming up to, 200 revs/min of stirring velocitys, react 6 hours at 100 DEG C of temperature, fluorine-containing amido silicon oil is obtained after cooling, this fluorine-containing amido silicon oil is even translucent thick liquid,
By above-mentioned obtained fluorine-containing amido silicon oil, add with the dimethylaminoethyl methacrylate of dissolve with ethanol, after being uniformly mixed, it is warming up to 25 DEG C, react 15 hours at 200 revs/min of stirring velocitys, 25 DEG C of temperature, obtaining the fluorine-containing amido silicon oil of modification, wherein, the primary amine of fluorine-containing amido silicon oil and the mol ratio of dimethylaminoethyl methacrylate are 1:1;
Another four mouthfuls of flasks add methyl chloride, it is warmed up to 65 DEG C, the fluorine-containing amido silicon oil adding above-mentioned modification is dripped while stirring under 200 revs/min of stirring velocitys, react after 5 hours, it is warmed up to 85 DEG C again, under same stirring velocity, continues reaction 1.5 hours, obtain the season fluorine-containing amido silicon oil of ammoniumization, wherein, in methyl chloride used and modified fluoride-containing amido silicon oil, the mol ratio of tertiary amine is 1:1;
At bath temperature 85 DEG C, drip and add acetic acid, by above-mentioned obtained season, the pH value of ammonium fluorine-containing organic silicon oil is adjusted to neutrality, then, is dissolved in 20 grams of deionized waters by emulsifying agent perfluoro capryl Tetrumethylammonium Iodide compound, slowly join in season ammonium fluorine-containing organic silicon oil while stirring, after adding, stir 1 hour under 1000 revs/min of stirring velocitys, obtain the homogeneous latex emulsion of season ammonium fluorine-containing organic silicon oil, wherein, the consumption of perfluoro capryl Tetrumethylammonium Iodide compound be season ammonium fluorine-containing organic silicon oil quality 0.5%.
Embodiment 4
Being joined by 50g octamethylcyclotetrasiloxane in four mouthfuls of flasks, add 0.3g potassium hydroxide, logical nitrogen, stirs evenly, at 145 DEG C of temperature, reacts 1 hour, obtained octamethylcyclotetrasiloxane linear body;
First 0.4g Tetramethylammonium hydroxide is dissolved in 32g deionized water, then, with 59.34g octamethylcyclotetrasiloxane linear body, 8gN-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, 0.6g end-capping reagent hexamethyldisiloxane joins together and agitator is housed, in four mouthfuls of flasks of reflux condensing tube and thermometer, it is uniformly mixed, lead to into nitrogen, then 100 DEG C it are warming up to, 200 revs/min of stirring velocitys, react 6 hours at 100 DEG C of temperature, fluorine-containing amido silicon oil is obtained after cooling, this fluorine-containing amido silicon oil is even translucent thick liquid,
By above-mentioned obtained fluorine-containing amido silicon oil, add with the dimethylaminoethyl methacrylate of dissolve with ethanol, after being uniformly mixed, it is warming up to 25 DEG C, react 15 hours at 200 revs/min of stirring velocitys, 25 DEG C of temperature, obtaining the fluorine-containing amido silicon oil of modification, wherein, the primary amine of fluorine-containing amido silicon oil and the mol ratio of dimethylaminoethyl methacrylate are 1:1;
Another four mouthfuls of flasks add methyl chloride, it is warmed up to 65 DEG C, the fluorine-containing amido silicon oil adding above-mentioned modification is dripped while stirring under 200 revs/min of stirring velocitys, react after 5 hours, it is warmed up to 85 DEG C again, under same stirring velocity, continues reaction 1.5 hours, obtain the season fluorine-containing amido silicon oil of ammoniumization, wherein, in methyl chloride used and modified fluoride-containing amido silicon oil, the mol ratio of tertiary amine is 1:1;
At bath temperature 85 DEG C, drip and add acetic acid, by above-mentioned obtained season, the pH value of ammonium fluorine-containing organic silicon oil is adjusted to neutrality, then, is dissolved in 20 grams of deionized waters by emulsifying agent perfluoro capryl Tetrumethylammonium Iodide compound, slowly join in season ammonium fluorine-containing organic silicon oil while stirring, after adding, stir 1 hour under 1000 revs/min of stirring velocitys, obtain the homogeneous latex emulsion of season ammonium fluorine-containing organic silicon oil, wherein, the consumption of perfluoro capryl Tetrumethylammonium Iodide compound be season ammonium fluorine-containing organic silicon oil quality 0.5%.
Embodiment 5
Being joined by 50g octamethylcyclotetrasiloxane in four mouthfuls of flasks, add 0.3g potassium hydroxide, logical nitrogen, stirs evenly, at 145 DEG C of temperature, reacts 1 hour, obtained octamethylcyclotetrasiloxane linear body;
Adding 50g trifluoro propyl methyl cyclotrisiloxane in another four mouthfuls of flasks, add 0.6g Tetramethylammonium hydroxide simultaneously, logical nitrogen, stirs evenly, at 155 DEG C of temperature, reacts 2 hours, obtained trifluoro propyl methyl cyclotrisiloxane linear body;
First 0.4g Tetramethylammonium hydroxide is dissolved in 32g deionized water, then, with 39.54g octamethylcyclotetrasiloxane linear body, 20g trifluoro propyl methyl cyclotrisiloxane linear body, 2gN-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, 0.6g end-capping reagent hexamethyldisiloxane joins together and agitator is housed, in four mouthfuls of flasks of reflux condensing tube and thermometer, it is uniformly mixed, lead to into nitrogen, then 100 DEG C it are warming up to, 200 revs/min of stirring velocitys, react 6 hours at 100 DEG C of temperature, fluorine-containing amido silicon oil is obtained after cooling, this fluorine-containing amido silicon oil is even translucent thick liquid,
By above-mentioned obtained fluorine-containing amido silicon oil, add with the dimethylaminoethyl methacrylate of dissolve with ethanol, after being uniformly mixed, it is warming up to 25 DEG C, react 15 hours at 200 revs/min of stirring velocitys, 25 DEG C of temperature, obtaining the fluorine-containing amido silicon oil of modification, wherein, the primary amine of fluorine-containing amido silicon oil and the mol ratio of dimethylaminoethyl methacrylate are 1:1;
Another four mouthfuls of flasks add methyl chloride, it is warmed up to 65 DEG C, the fluorine-containing amido silicon oil adding above-mentioned modification is dripped while stirring under 200 revs/min of stirring velocitys, react after 5 hours, it is warmed up to 85 DEG C again, under same stirring velocity, continues reaction 1.5 hours, obtain the season fluorine-containing amido silicon oil of ammoniumization, wherein, in methyl chloride used and modified fluoride-containing amido silicon oil, the mol ratio of tertiary amine is 1:1;
At bath temperature 85 DEG C, drip and add acetic acid, by above-mentioned obtained season, the pH value of ammonium fluorine-containing organic silicon oil is adjusted to neutrality, then, is dissolved in 20 grams of deionized waters by emulsifying agent perfluoro capryl Tetrumethylammonium Iodide compound, slowly join in season ammonium fluorine-containing organic silicon oil while stirring, after adding, stir 1 hour under 1000 revs/min of stirring velocitys, obtain the homogeneous latex emulsion of season ammonium fluorine-containing organic silicon oil, wherein, the consumption of perfluoro capryl Tetrumethylammonium Iodide compound be season ammonium fluorine-containing organic silicon oil quality 0.5%.
Embodiment 6
Being joined by 50g octamethylcyclotetrasiloxane in four mouthfuls of flasks, add 0.3g potassium hydroxide, logical nitrogen, stirs evenly, at 145 DEG C of temperature, reacts 1 hour, obtained octamethylcyclotetrasiloxane linear body;
Adding 50g trifluoro propyl methyl cyclotrisiloxane in another four mouthfuls of flasks, add 0.6g Tetramethylammonium hydroxide simultaneously, logical nitrogen, stirs evenly, at 155 DEG C of temperature, reacts 2 hours, obtained trifluoro propyl methyl cyclotrisiloxane linear body;
First 0.4g Tetramethylammonium hydroxide is dissolved in 32g deionized water, then, with 39.54g octamethylcyclotetrasiloxane linear body, 20g trifluoro propyl methyl cyclotrisiloxane linear body, 8gN-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, 0.6g end-capping reagent hexamethyldisiloxane joins together and agitator is housed, in four mouthfuls of flasks of reflux condensing tube and thermometer, it is uniformly mixed, lead to into nitrogen, then 100 DEG C it are warming up to, 200 revs/min of stirring velocitys, react 6 hours at 100 DEG C of temperature, fluorine-containing amido silicon oil is obtained after cooling, this fluorine-containing amido silicon oil is even translucent thick liquid,
By above-mentioned obtained fluorine-containing amido silicon oil, add with the dimethylaminoethyl methacrylate of dissolve with ethanol, after being uniformly mixed, it is warming up to 25 DEG C, react 15 hours at 200 revs/min of stirring velocitys, 25 DEG C of temperature, obtaining the fluorine-containing amido silicon oil of modification, wherein, the primary amine of fluorine-containing amido silicon oil and the mol ratio of dimethylaminoethyl methacrylate are 1:1;
Another four mouthfuls of flasks add monobromethane, it is warmed up to 65 DEG C, the fluorine-containing amido silicon oil adding above-mentioned modification is dripped while stirring under 200 revs/min of stirring velocitys, react after 5 hours, it is warmed up to 85 DEG C again, under same stirring velocity, continues reaction 1.5 hours, obtain the season fluorine-containing amido silicon oil of ammoniumization, wherein, in monobromethane used and modified fluoride-containing amido silicon oil, the mol ratio of tertiary amine is 1:1;
At bath temperature 85 DEG C, drip and add acetic acid, by above-mentioned obtained season, the pH value of ammonium fluorine-containing organic silicon oil is adjusted to neutrality, then, is dissolved in 20 grams of deionized waters by emulsifying agent perfluoro capryl Tetrumethylammonium Iodide compound, slowly join in season ammonium fluorine-containing organic silicon oil while stirring, after adding, stir 1 hour under 1000 revs/min of stirring velocitys, obtain the homogeneous latex emulsion of season ammonium fluorine-containing organic silicon oil, wherein, the consumption of perfluoro capryl Tetrumethylammonium Iodide compound be season ammonium fluorine-containing organic silicon oil quality 0.5%.
Embodiment 7
Being joined by 50g octamethylcyclotetrasiloxane in four mouthfuls of flasks, add 0.3g potassium hydroxide, logical nitrogen, stirs evenly, at 145 DEG C of temperature, reacts 1 hour, obtained octamethylcyclotetrasiloxane linear body;
Adding 50g trifluoro propyl methyl cyclotrisiloxane in another four mouthfuls of flasks, add 0.6g Tetramethylammonium hydroxide simultaneously, logical nitrogen, stirs evenly, at 155 DEG C of temperature, reacts 2 hours, obtained trifluoro propyl methyl cyclotrisiloxane linear body;
First 0.4g Tetramethylammonium hydroxide is dissolved in 32g deionized water, then, with 39.54g octamethylcyclotetrasiloxane linear body, 20g trifluoro propyl methyl cyclotrisiloxane linear body, 8gN-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, 0.1g end-capping reagent hexamethyldisiloxane joins together and agitator is housed, in four mouthfuls of flasks of reflux condensing tube and thermometer, it is uniformly mixed, lead to into nitrogen, then 100 DEG C it are warming up to, 200 revs/min of stirring velocitys, react 6 hours at 100 DEG C of temperature, fluorine-containing amido silicon oil is obtained after cooling, this fluorine-containing amido silicon oil is even translucent thick liquid,
By above-mentioned obtained fluorine-containing amido silicon oil, add with the dimethylaminoethyl methacrylate of dissolve with ethanol, after being uniformly mixed, it is warming up to 25 DEG C, react 15 hours at 200 revs/min of stirring velocitys, 25 DEG C of temperature, obtaining the fluorine-containing amido silicon oil of modification, wherein, the primary amine of fluorine-containing amido silicon oil and the mol ratio of dimethylaminoethyl methacrylate are 1:1;
Another four mouthfuls of flasks add methyl chloride, it is warmed up to 65 DEG C, the fluorine-containing amido silicon oil adding above-mentioned modification is dripped while stirring under 200 revs/min of stirring velocitys, react after 5 hours, it is warmed up to 85 DEG C again, under same stirring velocity, continues reaction 1.5 hours, obtain the season fluorine-containing amido silicon oil of ammoniumization, wherein, in methyl chloride used and modified fluoride-containing amido silicon oil, the mol ratio of tertiary amine is 1:1;
At bath temperature 85 DEG C, drip and add acetic acid, by above-mentioned obtained season, the pH value of ammonium fluorine-containing organic silicon oil is adjusted to neutrality, then, is dissolved in 20 grams of deionized waters by emulsifying agent perfluoro capryl Tetrumethylammonium Iodide compound, slowly join in season ammonium fluorine-containing organic silicon oil while stirring, after adding, stir 1 hour under 1000 revs/min of stirring velocitys, obtain the homogeneous latex emulsion of season ammonium fluorine-containing organic silicon oil, wherein, the consumption of perfluoro capryl Tetrumethylammonium Iodide compound be season ammonium fluorine-containing organic silicon oil quality 0.5%.
Embodiment 8
Being joined by 50g octamethylcyclotetrasiloxane in four mouthfuls of flasks, add 0.3g potassium hydroxide, logical nitrogen, stirs evenly, at 145 DEG C of temperature, reacts 1 hour, obtained octamethylcyclotetrasiloxane linear body;
Adding 50g trifluoro propyl methyl cyclotrisiloxane in another four mouthfuls of flasks, add 0.6g Tetramethylammonium hydroxide simultaneously, logical nitrogen, stirs evenly, at 155 DEG C of temperature, reacts 2 hours, obtained trifluoro propyl methyl cyclotrisiloxane linear body;
First 0.2g potassium hydroxide is dissolved in 32g deionized water, then, with 39.54g octamethylcyclotetrasiloxane linear body, 20g trifluoro propyl methyl cyclotrisiloxane linear body, 8gN-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, 0.6g end-capping reagent hexamethyldisiloxane joins together and agitator is housed, in four mouthfuls of flasks of reflux condensing tube and thermometer, it is uniformly mixed, lead to into nitrogen, then 100 DEG C it are warming up to, 200 revs/min of stirring velocitys, react 6 hours at 100 DEG C of temperature, fluorine-containing amido silicon oil is obtained after cooling, this fluorine-containing amido silicon oil is even translucent thick liquid,
By above-mentioned obtained fluorine-containing amido silicon oil, add with the dimethylaminoethyl methacrylate of dissolve with ethanol, after being uniformly mixed, it is warming up to 25 DEG C, react 15 hours at 200 revs/min of stirring velocitys, 25 DEG C of temperature, obtaining the fluorine-containing amido silicon oil of modification, wherein, the primary amine of fluorine-containing amido silicon oil and the mol ratio of dimethylaminoethyl methacrylate are 1:1;
Another four mouthfuls of flasks add methyl chloride, it is warmed up to 65 DEG C, the fluorine-containing amido silicon oil adding above-mentioned modification is dripped while stirring under 200 revs/min of stirring velocitys, react after 5 hours, it is warmed up to 85 DEG C again, under same stirring velocity, continues reaction 1.5 hours, obtain the season fluorine-containing amido silicon oil of ammoniumization, wherein, in methyl chloride used and modified fluoride-containing amido silicon oil, the mol ratio of tertiary amine is 1:1;
At bath temperature 85 DEG C, drip and add acetic acid, by above-mentioned obtained season, the pH value of ammonium fluorine-containing organic silicon oil is adjusted to neutrality, then, is dissolved in 20 grams of deionized waters by emulsifying agent perfluoro capryl Tetrumethylammonium Iodide compound, slowly join in season ammonium fluorine-containing organic silicon oil while stirring, after adding, stir 1 hour under 1000 revs/min of stirring velocitys, obtain the homogeneous latex emulsion of season ammonium fluorine-containing organic silicon oil, wherein, the consumption of perfluoro capryl Tetrumethylammonium Iodide compound be season ammonium fluorine-containing organic silicon oil quality 0.5%.
It is after 1:20 adds water by bath raio, do not add respectively and increase season ammonium fluorine-containing organic silicon emulsion obtained in dark finishing composition, common organic silicon emulsion and embodiment 1-embodiment 8, wherein, obtained in common organic silicon emulsion and embodiment 1-embodiment 8 season, the consumption of ammonium fluorine-containing organic silicon emulsion was the 5% of black terylene fabric weight. Then, after being warmed up to 60 DEG C of running 20min, go out cylinder, dehydration, dry, then at the air dry oven of 120 DEG C of temperature dry 5 minutes, the air dry oven training 180 DEG C of temperature is dried 40 seconds, puts flat, get damp again after cooling after taking-up on desktop. Tested by Datacolor color measurement instrument, and the method adopting Xu Muqing " printing and dyeing examination chemical examination " document, GB/T4802.3-2008, GB/T3921.1��5-2008 and GB/T8424.1��3-2001 to specify detects, and the results are shown in Table 1.
Table 1 does not add finishing composition and adds the Performance comparision table of fabric after finishing composition
As can be known from Table 1, compare not add and increase dark finishing composition and add common organic silicon emulsion, by the season easier emulsification of ammonium fluorine-containing organic silicon oil that present method is obtained, and the emulsion formed is comparatively stable, black terylene fabric is had and significantly increases dark effect, yarn fabric also has good flexibility simultaneously, and has good anti-fluffing and anti-pilling performance and good persistence.
Each technology feature of the above embodiment can combine arbitrarily, for making description succinct, each all possible combination of technology feature in above-described embodiment is not all described, but, as long as the combination of these technology features does not exist contradiction, all it is considered to be the scope that this specification sheets is recorded.
The above embodiment only have expressed several enforcement modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be construed as limiting the scope of the patent. , it is also possible to make some distortion and improvement, it should be appreciated that for the person of ordinary skill of the art, without departing from the inventive concept of the premise these all belong to protection scope of the present invention. Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. one kind increases the preparation method of dark finishing composition, it is characterised in that, comprise step:
1) by the aqueous solution of strong alkali catalyst, octamethylcyclotetrasiloxane linear body, trifluoro propyl methyl cyclotrisiloxane linear body, ammonia type coupling agent and end-capping reagent mixing, stir after evenly, lead to into nitrogen, at 180-200 rev/min of stirring velocity, 100-110 DEG C of temperature, react 4-8 hour, obtaining fluorine-containing amido silicon oil, wherein, the weight percentage of above-mentioned raw materials is:
2) by described fluorine-containing amido silicon oil, the dimethylaminoethyl methacrylate of dissolve with ethanol mixes with adopting in advance, stir after evenly, at 180-200 rev/min of stirring velocity, 20-30 DEG C of temperature, react 12-20 hour, obtain the fluorine-containing amido silicon oil of modification, wherein, the mol ratio of the primary amino in described fluorine-containing amido silicon oil and described dimethylaminoethyl methacrylate is 1:1-1:1.15;
3) under 55-75 DEG C of temperature, 180-200 rev/min of stirring velocity, haloalkane drips fluorine-containing amido silicon oil while stirring that add described modification, and react 3-6 hour, then, continue to heat up, at 180-200 rev/min of stirring velocity, 75-80 DEG C of temperature, continue reaction 1-2 hour, obtaining season ammonium fluorine-containing organic silicon oil, wherein, the mol ratio of the tertiary amine groups in the fluorine-containing amido silicon oil of described haloalkane and described modification is 1:0.8-1:1.2;
4) at 85 DEG C of temperature, by described season, the PH value of ammonium fluorine-containing organic silicon oil is adjusted to 7, again the emulsifying agent being dissolved in advance in 20 grams of deionized waters is added to while stirring in described season ammonium fluorine-containing organic silicon oil, react 1 hour under 900-1200 rev/min of stirring velocity, obtain the season ammonium fluorine-containing organic silicon oil of emulsification, wherein, the quality of described emulsifying agent is the 0.1%-2% of quality of described season ammonium fluorine-containing organic silicon oil.
2. the preparation method of the dark finishing composition of increasing according to claim 1, it is characterized in that, in described step 1) in described ammonia type coupling agent be at least one in N-��-(aminoethyl)-��-aminopropyl methyl dimethoxysilane, ��-aminopropyl methyl dimethoxysilane.
3. the preparation method of the dark finishing composition of increasing according to claim 1, it is characterised in that, in described step 1) in described end-capping reagent be hexamethyldisiloxane or pentamethyl disiloxane.
4. the preparation method of the dark finishing composition of increasing according to claim 1, it is characterized in that, described step 1) in described octamethylcyclotetrasiloxane linear body obtain in the following manner: octamethylcyclotetrasiloxane and potassium hydroxide are mixed, stir after evenly, lead to into nitrogen, at 200-400 rev/min of stirring velocity, 140-150 DEG C of temperature, react 0.5-3 hour, obtain described octamethylcyclotetrasiloxane linear body, wherein, the quality of described potassium hydroxide is the 0.1%-0.5% of the quality of described octamethylcyclotetrasiloxane.
5. the preparation method of the dark finishing composition of increasing according to claim 1, it is characterized in that, in described step 1) in described trifluoro propyl methyl cyclotrisiloxane linear body obtain in the following manner: trifluoro propyl methyl cyclotrisiloxane and Tetramethylammonium hydroxide are mixed, stir after evenly, lead to into nitrogen, 200-400 rev/min of stirring velocity, at 150-160 DEG C of temperature, react 1-5 hour, obtain described trifluoro propyl methyl cyclotrisiloxane linear body, wherein, the quality of described Tetramethylammonium hydroxide is the 0.3%-1% of the quality of described trifluoro propyl methyl cyclotrisiloxane.
6. the preparation method of the dark finishing composition of increasing according to claim 1, it is characterised in that, in described step 3) in the general formula of described haloalkane be: CH3(CH2)n-X, n are integer, and n is more than or equal to 0, and to be less than or equal to 8, X be halogen atom.
7. the preparation method of the dark finishing composition of increasing according to claim 1, it is characterised in that, in described step 4) in, by adding acetic acid, by described step 3) in obtain season ammonium fluorine-containing organic silicon oil PH value be adjusted to 7.
8. the preparation method of the dark finishing composition of increasing according to claim 1, it is characterised in that, in described step 4) in described emulsifying agent be fluorine-containing emulsifier.
9. the preparation method of the dark finishing composition of increasing according to claim 8, it is characterised in that, described fluorine-containing emulsifier is at least one in fluorine ether, oxyethyl group class non-ionic type fluorocarbon surfactant and perfluoro capryl Tetrumethylammonium Iodide compound.
10. one kind increases dark finishing composition, it is characterised in that, the dark finishing composition of described increasing is season ammonium fluorine-containing organic silicon oil, described season the structural formula of ammonium fluorine-containing organic silicon oil be:
In described structural formula, x, y, z is positive integer; The general formula of R is CH3(CH2) n, wherein, n is integer, and n is more than or equal to 0, and to be less than or equal to 8, X be halogen atom.
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