CN103030814B - Washable hydrophilic silicone oil and preparation method thereof - Google Patents
Washable hydrophilic silicone oil and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of silicone oil processing, and particularly relates to washable hydrophilic silicone oil and a preparation method thereof. The washable hydrophilic silicone oil comprises a main component of block polyether quaternary ammonium salt silicone oil, with a structural formula shown in the specification. In the structural formula R1 is shown in the specification, in which a is equal to 10-2000; in the structural formula, R2 is shown in the specification, in which b is equal to 10-2000, p is equal to 10-500, q is equal to 10-500, a sum of p and q is equal to 20-1000; in the structural formula, R3 is shown in the specification; and in the structural formula, m is equal to a sum of m1, m2 and m3 or a sum of m4, m5 and m6, m is equal to 15-600, m1 is equal to 5-200, m2 is equal to 5-200, m3 is equal to 5-200, m4 is equal to 5-200, m5 is equal to 5-200, and m6 is equal to 5-200. The washable hydrophilic silicone oil is resistant to alkali, electrolyte and high temperature; the washability of the silicone oil can be improved; cotton fabric processed by the silicone oil is good in softness and smoothness and strong in hydrophily; and the preparation method has the characteristics of simple process conditions and easiness in operation.
Description
Technical field
The invention belongs to silicone oil processing technique field, particularly a kind of Washable hydrophilic silicone oil and preparation method thereof.
Background technology
At present, cotton fabric is after hydrophilic silicone oil arranges, feel is sliding soft, hydrophilic, improve the wear behavior of fabric, but after washing several times, silicone oil can by eccysis from fabric, feel is caused to be deteriorated, wear behavior declines, and therefore, the exploitation of Washable hydrophilic silicone oil will have great importance and market outlook.
The measure promoting silicone oil washing fastness mainly contains, and one side is direct introduces active group, as amino, hydroxyl etc. in silicone molecule, these groups can with the hydroxyl reaction on cotton fibre, form hydrogen bond, thus improve the sticking power of silicone oil on fabric, also improve washing fastness with regard to corresponding; On the other hand, increase the reactivity of silicone oil self, make it in textile finishing processes, self-crosslinking becomes macromole, film forming on fabric, adds by the difficulty of eccysis, also just improves washing fastness; Moreover introduce as epoxy group(ing), epoxy group(ing) etc. can form the reactive group of covalent linkage with the hydroxyl reaction in cotton fibre, but this kind of measure, unsatisfactory in actual applications, because the condition of epoxy group(ing) and hydroxyl reaction is harsher, there is use limitation.
In addition, existing hydrophilic silicone oil is alkaline-resisting, electrolyte res is tance is poor, especially in high ph-values, polyelectrolyte, under high temperature, as 80 DEG C, more easily there is breakdown of emulsion in working fluid, the problems such as wadding of wafing, and therefore requires higher to working conditions, can only use under slightly acidic or neutrallty condition.
For cotton fabric by utilizing reactive dye dyeing and upper soft after, if fabric need repair look, there is the problems such as alkaline-resisting, electrolyte-resistant is poor in some hydrophilic silicone oil, needs first to be divested by silicone oil before therefore repairing look, in order to avoid silicone oil breakdown of emulsion, waft wadding, occurs the problems such as silicone oil spot; Existing hydrophilic silicone oil to after soft on cotton fabric, the problem that ubiquity colour fastness to washing declines.
Chinese invention patent, application number is 201110413665.1, denomination of invention is the preparation method of quaternary copolymer block organic silicon oil, take polysiloxane as main raw material, by with Piperazine anhydrous, Amino Terminated polyether(ATPE) reaction forms, solve silicone oil and cause xanthochromia, the problem of wetting ability and stability, still not enough with the avidity of cotton fibre, washing fastness still needs to improve, in addition, strong ionic group is lacked in silicone molecule structure in patent, therefore intermolecular electrostatic repulsion is low, under high ph-values or polyelectrolyte condition, during high temperature, silicone molecule is easily assembled, separate out, there is floating oil, to waft the problems such as wadding.
Patent of invention CN1106833A, denomination of invention is containing replace 1,3, the organopolysiloxane of 5-5-triazine units, 1,3 of access band halogen atom, 5-5-triazine units, improve the washing fastness on cotton fabric, but it needs dispersion agent or emulsifying agent just can be scattered in water, therefore there is the problem of breakdown of emulsion, roll banding, in addition, there is the problem of resistance to alkali cleaning and not resistance to pickling in the covalent linkage that s-triazine active group and cotton fibre are formed, i.e. acid lower facile hydrolysis scission of link, causes the coming off of silicone oil, washing fastness declines.
In general, above-mentioned several approach, although the washing fastness of silicone oil can be improved to a certain extent, the washable number of times of home washings is increased to 5-15 time, but promote effect and expect that requirement still has gap, as in alkaline washing, hydrogen bond etc. are easily destroyed, cause silicone oil to come off, feel be deteriorated, washing fastness decline.In addition, hydrophilic silicone oil alkali stability, freeze thaw stability, also badly solution is needed to problems such as the disadvantageous effects of colour fastness to washing.
Summary of the invention
The object of the present invention is to provide a kind of Washable hydrophilic silicone oil, make it have:
1. dyeing with bathing use with cotton fabric by utilizing reactive dye, there is effect soft in bath, prevent cotton fabric from dyeing, occurring a difficult problem for fold;
2. alkaline-resisting, electrolyte-resistant, resistant to elevated temperatures stable performance, improves silicone oil washing fastness;
3., when look repaiied by cotton fabric, can directly strip or change colour;
4. self-emulsifying of the present invention, there will not be the problem of breakdown of emulsion, roll banding;
5. silicone oil of the present invention does not make colour fastness to washing decline, and has certain tint retention concurrently.
Another object of the present invention is to the preparation method providing a kind of Washable hydrophilic silicone oil, it is simple that it has preparation process condition, easy to operate, the feature that reaction effect is good.
For achieving the above object, the present invention adopts following technical proposals:
A kind of Washable hydrophilic silicone oil, its bulk composition is block polyether quaternary ammonium salt silicone oil, and its structural formula is as follows:
，
In described structural formula, R
1for
, wherein a=10-2000,
R in described structural formula
2for
，
Wherein, b=10-2000, p=10-500, q=10-500, p+q=20-1000,
R in described structural formula
3for
;
In described structural formula, m=m
1+ m
2+ m
3=m
4+ m
5+ m
6, m=15-600, m
1=5-200, m
2=5-200, m
3=5-200, m
4=5-200, m
5=5-200, m
6=5-200.
Further, in described structural formula: a=20-500, b=20-500, p=100-350, q=100-350, p+q=200-700, m
1=15-120, m
2=15-120, m
3=15-120, m
4=15-120, m
5=15-120, m
6=15-120, m=45-360.
The Washable hydrophilic silicone oil of structure above forms primarily of following raw material reaction:
Component A: terminal hydroxy group linear body silicone oil or hexamethyl cyclotrisiloxane or octamethylcyclotetrasiloxane;
B component: piperizinylmethyl dimethoxysiloxane, both-end epoxy polyoxyethylene poly-oxygen propylene aether,
3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, difluoro dichloro pyrimidine;
C component: basic catalyst.
Wherein, the structural formula of each component is as follows respectively:
Terminal hydroxy group linear body silicone oil:
, n represents the polymerization degree, n=5-500,
Hexamethyl cyclotrisiloxane:
,
Octamethylcyclotetrasiloxane:
,
Piperizinylmethyl dimethoxysiloxane:
,
Both-end epoxy polyoxyethylene poly-oxygen propylene aether:
,
p=10-500,q=10-500，p+q=20-1000，
3-chloro-2-hydroxypropyl-trimethyl ammonium chloride:
,
Difluoro dichloro pyrimidine:
.
The reaction mechanism of the Washable hydrophilic silicone oil of structure above is:
1, under the effect of basic catalyst, terminal hydroxy group linear body silicone oil and piperizinylmethyl dimethoxysiloxane pass through transesterification reaction, change terminal hydroxy group amido silicon oil into, addition reaction is passed through again with both-end epoxy polyoxyethylene poly-oxygen propylene aether, change terminal hydroxy group amino-polyether silicone oil into, and then pass through nucleophilic substitution reaction with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, quaternary ammonium salt is connected on the secondary amino group in part piperazinyl, finally add difluoro dichloro pyrimidine, pass through nucleophilic substitution reaction, difluoro dichloro pyrimidine active group is connected on the secondary amino group in part piperazinyl, obtain block polyether quaternary ammonium salt silicone oil.
2, under basic catalyst effect, hexamethyl cyclotrisiloxane changes hexamethyl dihydroxyl trisiloxanes into, by intermolecular dehydration, further polycondensation is low-molecular-weight end hydroxyl silicone oil, transesterification reaction is passed through again with piperizinylmethyl dimethoxysiloxane, change terminal hydroxy group amido silicon oil into, addition reaction is passed through again with both-end epoxy polyoxyethylene poly-oxygen propylene aether, change terminal hydroxy group amino-polyether silicone oil into, and then pass through nucleophilic substitution reaction with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, quaternary ammonium salt is connected on the secondary amino group in part piperazinyl, finally add difluoro dichloro pyrimidine, pass through nucleophilic substitution reaction, difluoro dichloro pyrimidine active group is connected on the secondary amino group in part piperazinyl, obtain block polyether quaternary ammonium salt silicone oil.
3, under basic catalyst effect, octamethylcyclotetrasiloxane changes prestox dihydroxyl tetrasiloxane into, by intermolecular dehydration, further polycondensation is low-molecular-weight end hydroxyl silicone oil, transesterification reaction is passed through again with piperizinylmethyl dimethoxysiloxane, change terminal hydroxy group amido silicon oil into, addition reaction is passed through again with both-end epoxy polyoxyethylene poly-oxygen propylene aether, change terminal hydroxy group amino-polyether silicone oil into, and then pass through nucleophilic substitution reaction with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, quaternary ammonium salt is connected on the secondary amino group in part piperazinyl, finally add difluoro dichloro pyrimidine, pass through nucleophilic substitution reaction, difluoro dichloro pyrimidine active group is connected on the secondary amino group in part piperazinyl, obtain block polyether quaternary ammonium salt silicone oil.
Further, its concrete reactions steps is as follows:
1st step, drops into the terminal hydroxy group linear body silicone oil of 0.2mol, 0.85g potassium hydroxide, 0.04mol piperizinylmethyl dimethoxysiloxane, is warming up to 90-95 DEG C in reactor, reacts 3 hours;
2nd step, drop into 0.075mol both-end epoxy polyoxyethylene poly-oxygen propylene aether, 90-95 DEG C is continued reaction 3.5 hours;
3rd step, is cooled to 80-85 DEG C, drops into 0.008mol 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, reacts 3.5 hours;
4th step, is cooled to 40-45 DEG C, drops into 0.004mol difluoro dichloro pyrimidine, reacts 3 hours, namely obtain block polyether quaternary ammonium salt silicone oil.
Further, its to use hexamethyl cyclotrisiloxane to prepare the concrete reactions steps of block polyether quaternary ammonium salt silicone oil as follows:
1st step, drops into the hexamethyl cyclotrisiloxane of 0.5mol, 0.6mol deionized water, 1g potassium hydroxide, is warming up to 80-85 DEG C in reactor, reacts 0.5 hour;
2nd step, drops into 0.05mol piperizinylmethyl dimethoxysiloxane, is warming up to 120-125 DEG C, reacts 3.5 hours;
3rd step, is cooled to 85-90 DEG C, drops into 0.08mol both-end epoxy polyoxyethylene poly-oxygen propylene aether, continues reaction 3 hours,
4th step, is cooled to 80-85 DEG C, drops into 0.01mol 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, reacts 3 hours;
5th step, is cooled to 40-45 DEG C, drops into 0.005mol difluoro dichloro pyrimidine, reacts 3 hours, namely obtain block polyether quaternary ammonium salt silicone oil.
Further, its to use octamethylcyclotetrasiloxane to prepare the concrete reactions steps of block polyether quaternary ammonium salt silicone oil as follows:
1st step, drops into the octamethylcyclotetrasiloxane of 0.7mol, 0.85mol deionized water, 1g potassium hydroxide, is warming up to 80-85 DEG C in reactor, reacts 0.5 hour;
2nd step, drops into 0.075mol piperizinylmethyl dimethoxysiloxane, is warming up to 120-125 DEG C, reacts 3.5 hours;
3rd step, is cooled to 85-90 DEG C, drops into 0.12mol both-end epoxy polyoxyethylene poly-oxygen propylene aether, continues reaction 3 hours,
4th step, is cooled to 80-85 DEG C, drops into 0.015mol 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, reacts 3 hours;
5th step, is cooled to 30-35 DEG C, drops into 0.0065mol difluoro dichloro pyrimidine, reacts 3 hours, namely obtain block polyether quaternary ammonium salt silicone oil.
Beneficial effect of the present invention is: 1. product belongs to hydrophilic silicone oil, the wetting ability of cotton fabric can be improved or wetting ability is had no adverse effect, fabric after arrangement has comfortable sense of touch, soft, smooth, fine and smooth, fluffy, has ability of sweat absorption, makes comfortable and easy to wear.
2. self-emulsifying, does not need during use to add dispersion agent or emulsifying agent, with deionized water, silicone oil stoste is diluted to concentration 20% or 30%, can directly uses, there will not be breakdown of emulsion, roll banding problem in using.
3. good stability, acid and alkali-resistance (pH=3-13), electrolyte-resistant, high temperature resistant (100 DEG C not floating oil), resistant to shearing, resistance to centrifugal (not stratified).
4. acid and alkali-resistance, electrolyte res is tance excellence, can with bathe use in cotton fabric by utilizing reactive dye dyeing; With cotton fabric dyeing process with bathing use, effect soft in bath can be played, avoid cotton fabric to occur the difficult problems such as wrinkle, folding line and deadfold, when therefore using with bath, no longer can add wetting softener, reduce production cost.
5. silicone oil and cotton fabric by utilizing reactive dye are same in dyeing bathes use, goes up soft arrangement again, shorten technical process after not needing dyeing.
6. there is active group in silicone molecule, active group can react with the hydroxyl on cotton fibre, form covalent linkage under alkalescence, makes silicone oil anchor on cotton fibre, therefore can ensure that silicone oil is retained on fabric for a long time, improve washing fastness.
7. silicone oil is to after soft on cotton fabric, has certain tint retention, colour fastness to washing can not be caused to decline.
Another beneficial effect of the present invention is: preparation method is easy and simple to handle, and reaction conditions is content with very little and controls, and reduces costs, and enhances productivity.
Functional group type in product structure and function thereof:
1): products molecule structure end hydroxyl active group, therefore in finish fabric process dry or when baking, can dehydrated crosslinking between hydroxyl, silicone molecule is made to be cross-linked into macromole, in fiber surface film forming, not only increase slippery, also have coating function to the non-bonding on fiber or the reactive dyestuffs that have been hydrolyzed, stop dyestuff to come off from fiber, play certain colour fixation.
2): containing amino in products molecule structure, give product good pliability.
3): containing quaternary ammonium group in products molecule structure, the avidity with cotton fibre can be increased on the one hand, improve the adsorption rate on cotton fibre, also helpful to colour fastness to washing; On the other hand, quaternary ammonium group cation group enhances electrostatic repulsion between silicone molecule, reduces the gathering tendency between silicone molecule, thus can ensure the dispersion stabilization under high temperature, alkalescence, polyelectrolyte environment; Moreover, introduce quaternary ammonium group in silicone molecule, also have castering action to performance, softness, loft and wetting ability can be improved.
4): containing polyoxyethylene, polyoxypropylene group in products molecule structure, give product wetting ability on the one hand, make the cotton fabric after arrangement have excellent wetting ability, ability of sweat absorption, keep natural hydrophilic style; Moreover the polyether group in molecular structure makes silicone oil self-emulsifying, certainly dispersion, and does not need to relend assistant for emulsifying agent or dispersion agent, achieves the object that used water in use is directly diluted.Owing to being self-emulsifying silicone oil and for block structure, the cotton fabric therefore after it arranges, sliding soft, dry and comfortable, the non-greasy of feel, does not damage cotton natural hand style.
5): containing pyrimidine active group in products molecule structure, pyrimidine group is (pH value=10-12) in the basic conditions, can with the hydroxyl generation nucleophilic substitution reaction on cotton fibre, form covalent linkage, silicone molecule and cotton fibre are combined, improves silicone oil fastness to washing, ensure that washing fastness.
Embodiment
With specific embodiment, the present invention is further illustrated below, but the present invention is not by the restriction of following embodiment.
embodiment
1
.
Main employing hexamethyl cyclotrisiloxane and difluoro dichloro pyrimidine prepare block polyether quaternary ammonium salt silicone oil.
1st step, drops into the hexamethyl cyclotrisiloxane of 0.5mol, 0.6mol deionized water, 1g potassium hydroxide, is warming up to 80-85 DEG C in reactor, reacts 0.5 hour;
2nd step, drops into 0.05mol piperizinylmethyl dimethoxysiloxane, is warming up to 120-125 DEG C, reacts 3.5 hours;
3rd step, is cooled to 85-90 DEG C, drops into 0.08mol both-end epoxy polyoxyethylene poly-oxygen propylene aether, continues reaction 3 hours,
4th step, is cooled to 80-85 DEG C, drops into 0.01mol 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, reacts 3 hours;
5th step, is cooled to 40-45 DEG C, drops into 0.005mol difluoro dichloro pyrimidine, reaction 3 hours, namely obtains block polyether quaternary ammonium salt silicone oil.
In whole reaction process, relate to principal reaction formula as follows:
1st step reaction:
，
2nd step reaction:
，
3rd step reaction:
,
A represents the product end hydroxyl amino silicone oil of second step reaction, as follows:
，
E represents raw material both-end epoxy polyoxyethylene poly-oxygen propylene aether, as follows:
4th step reaction:
，
5th step reaction:
，
R
1representative:
, wherein, a=20-200,
R
2representative:
, wherein b=20-200, p=100-300, q=100-300, p+q=200-600.
m=m
1+m
2+m
3=m
4+m
5+m
6，m=45-180，m
1=15-60，m
2=15-60，m
3=15-60，m
4=15-60，m
5=15-60，m
6=15-60。
embodiment
2
.
Main employing octamethylcyclotetrasiloxane and difluoro dichloro pyrimidine prepare block polyether quaternary ammonium salt silicone oil.
1st step, drops into the octamethylcyclotetrasiloxane of 0.7mol, 0.85mol deionized water, 1g potassium hydroxide, is warming up to 80-85 DEG C in reactor, reacts 0.5 hour;
2nd step, drops into 0.075mol piperizinylmethyl dimethoxysiloxane, is warming up to 120-125 DEG C, reacts 3.5 hours;
3rd step, is cooled to 85-90 DEG C, drops into 0.12mol both-end epoxy polyoxyethylene poly-oxygen propylene aether, continues reaction 3 hours,
4th step, is cooled to 80-85 DEG C, drops into 0.015mol 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, reacts 3 hours;
5th step, is cooled to 40-45 DEG C, drops into 0.0065mol difluoro dichloro pyrimidine, reacts 3.5 hours, namely obtain block polyether quaternary ammonium salt silicone oil.
In whole reaction process, relate to principal reaction formula as follows:
1st step reaction:
，
2nd step reaction:
，
3rd step reaction:
,
B represents the product end hydroxyl amino silicone oil of second step reaction, as follows:
，
E represents raw material both-end epoxy polyoxyethylene poly-oxygen propylene aether, as follows:
，
4th step reaction:
，
5th step reaction:
，
R
1representative:
, wherein, a=60-400,
R
2representative:
，
Wherein, b=60-400, m=m
1+ m
2+ m
3=m
4+ m
5+ m
6, m=90-270, m
1=30-90, m
2=30-90, m
3=30-90, m
4=30-90, m
5=30-90, m
6=30-90, p=150-350, q=150-350, p+q=300-700.
embodiment
3
.
Main employing terminal hydroxy group linear body silicone oil and difluoro dichloro pyrimidine prepare block polyether quaternary ammonium salt silicone oil.
1st step, drops into the terminal hydroxy group linear body silicone oil of 0.2mol, 0.85g potassium hydroxide, 0.04mol piperizinylmethyl dimethoxy silane, is warming up to 90-95 DEG C in reactor, reacts 3 hours;
2nd step, drop into 0.075mol both-end epoxy polyoxyethylene poly-oxygen propylene aether, 90-95 DEG C is continued reaction 3.5 hours;
3rd step, is cooled to 80-85 DEG C, drops into 0.008mol 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, reacts 3.5 hours;
4th step, is cooled to 40-45 DEG C, drops into 0.004 mol difluoro dichloro pyrimidine, reacts 3.5 hours, namely obtains block polyether quaternary ammonium salt silicone oil.
In whole reaction process, relate to principal reaction formula as follows:
1st step reaction:
，
2nd step reaction:
,
C represents the product end hydroxyl amino silicone oil of second step reaction, as follows:
E represents raw material both-end epoxy polyoxyethylene poly-oxygen propylene aether, as follows:
3rd step reaction:
4th step reaction:
R
1representative:
, wherein, a=200-500,
R
2representative:
，
Wherein, n=10-200, b=200-500, p+q=240-560, p=120-280, q=120-280, m=m
1+ m
2+ m
3=m
4+ m
5+ m
6, m=120-360, m
1=40-120, m
2=40-120, m
3=40-120, m
4=40-120, m
5=40-120, m
6=40-120.
performance comparison:
1, colour examining change, colour fastness to washing and washing fastness.
The block polyether quaternary ammonium salt silicone oil deionized water that embodiment one or embodiment two or embodiment three are synthesized is opened rare for massfraction be 30% silicone oil dispersion liquid, by following prescription and technique and Dyeing of Cotton Fabric with Reactive Dyes knitted fabrics, above softly to carry out with bathing:
Reactive red M-2B 3%(o.w.f)
Silicone oil 0%, 1.5%(o.w.f)
Sodium sulfate anhydrous.min(99) 60g/L
Soda ash 15g/L
Bath raio 1:10, adopt constant temperature method dyeing, temperature 60 C, time 60min, then washes, soaps, washes, neutralizes, dewaters, dries, colour examining change, colour fastness to washing and washing fastness.
Result is as shown in table 1: dyeing, upper soft bathe together the cotton fabrics contaminated color and luster, coloured light and do not add that silicone oil dyes suitable, illustrate that employing has no adverse effect to dyeing substantially with bath method.
Choose commercially available 1, commercially available 2 hydrophilic silicone oils and silicone oil of the present invention, respectively opening rare one-tenth massfraction is the emulsion of 30%, goes up soft arrangement as follows:
Silicon oil dosage: 1.5%(o.w.f), bath raio 1:10, temperature controls at 40 DEG C, and then time 15min dewaters, dries, colour examining change, colour fastness to washing and washing fastness.
Look becomes, colour fastness to washing and washing fastness are correlated with concrete data, as follows:
Table 1 look becomes, colour fastness to washing
| Look becomes (△ E) | Colour fastness to washing | |
| Before upper soft arrangement | Standard | 4-5 |
| Soft on commercially available 1 | 0.21 | 4 |
| Soft on commercially available 2 | 0.45 | 3-4 |
| Soft on silicone oil of the present invention | 0.23 | 4-5 |
Test washing fastness (washfastness test method is: with synthetic detergent 4g/L, soda ash 1g/L, wash 5min, be designated as and wash once in the water of 40 DEG C).
As shown in table 2 below by test wash durability results: before washing, the softness of silicone oil of the present invention, slippery, loft feel are substantially suitable with commercially available silicone oil, but after being above 10 washings, commercially available silicone oil is substantially without feel, and the feel of silicone oil of the present invention with washing before substantially suitable, washable 30 times of silicone oil of the present invention, fabric feeling declines still little, illustrates that silicone oil of the present invention has excellent washing fastness.
Table 2 washing fastness
Note: 1-5 represents feel degree, and 1 to represent feel degree the poorest, and 5 to represent feel degree best.
2, stability test
The block polyether quaternary ammonium salt silicone oil deionized water that embodiment one, embodiment two, embodiment three are synthesized open rare for massfraction be 30% silicone oil dispersion liquid, by commercially available 1, commercially available 2 hydrophilic silicone oils, opening rare one-tenth massfraction is the emulsion of 30%, test high thermal resistance, resistance to acids and bases, electrolyte-resistant, resistant to shearing and resistance to dewatering ability.
By testing the result of high temperatures, resistance to acids and bases, electrolyte-resistant, resistant to shearing and resistance to dewatering ability as shown in following table 3-8: show that above-mentioned every stability of silicone oil of the present invention is better than commercially available hydrophilic silicone oil.
Table 3 heat-resistant stable
Note: 1., during test, deposit 2 hours at different temperatures,
2. working fluid is configured to 20g/L.
Table 4 acid-resistant stability
Note: 1., during test, deposit 2 hours at different temperatures,
2. working fluid is configured to 20g/L.
Table 5 alkali stability
Note: 1., during test, deposit 2 hours at different temperatures,
2. working fluid is configured to 20g/L.
Table 6 Stability towards electrolytes
Note: 1., during test, deposit 2 hours at different temperatures,
2. working fluid is configured to 20g/L.
Table 7 resistant to shearing stability
Note: 1. room temperature test,
2. working fluid is configured to 20g/L.
The resistance to dewatering ability of table 8
Note: 1. room temperature test,
2. working fluid is configured to 20g/L.
The above is only preferred embodiment of the present invention, therefore all equivalences done according to structure, feature and the principle described in patent claim of the present invention change or modify, and are included in patent claim of the present invention.
Claims (9)
1. a Washable hydrophilic silicone oil, is characterized in that: bulk composition is block polyether quaternary ammonium salt silicone oil, and its structural formula is as follows:
In described structural formula, R
1for
, wherein a=10-2000,
In described structural formula, R
2for
，
Wherein, b=10-2000, p=10-500, q=10-500, p+q=20-1000,
In described structural formula, R
3for
;
In described structural formula, m=m
1+ m
2+ m
3=m
4+ m
5+ m
6, m=15-600, m
1=5-200, m
2=5-200, m
3=5-200, m
4=5-200, m
5=5-200, m
6=5-200,
By nucleophilic substitution reaction, difluoro dichloro pyrimidine active group is connected on the secondary amino group in part piperazinyl, obtains block polyether quaternary ammonium salt silicone oil.
2. a kind of Washable hydrophilic silicone oil according to claim 1, is characterized in that: in described structural formula: a=20-500, b=20-500, p=100-350, q=100-350, p+q=200-700, m
1=15-120, m
2=15-120, m
3=15-120, m
4=15-120, m
5=15-120, m
6=15-120, m=45-360.
3. the preparation method of a kind of Washable hydrophilic silicone oil described in any one of claim 1-2, is characterized in that: form primarily of following raw material reaction:
Component A: terminal hydroxy group linear body silicone oil or hexamethyl cyclotrisiloxane or octamethylcyclotetrasiloxane;
B component: piperizinylmethyl dimethoxysiloxane, both-end epoxy polyoxyethylene poly-oxygen propylene aether,
3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, difluoro dichloro pyrimidine;
C component: potassium hydroxide basic catalyzer.
4. the preparation method of a kind of Washable hydrophilic silicone oil according to claim 3, it is characterized in that: under the effect of basic catalyst, terminal hydroxy group linear body silicone oil and piperizinylmethyl dimethoxysiloxane pass through transesterification reaction, change terminal hydroxy group amido silicon oil into, addition reaction is passed through again with both-end epoxy polyoxyethylene poly-oxygen propylene aether, change terminal hydroxy group amino-polyether silicone oil into, and then pass through nucleophilic substitution reaction with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, quaternary ammonium salt is connected on the secondary amino group in part piperazinyl, finally add difluoro dichloro pyrimidine, pass through nucleophilic substitution reaction, difluoro dichloro pyrimidine active group is connected on the secondary amino group in part piperazinyl, obtain block polyether quaternary ammonium salt silicone oil.
5. the preparation method of a kind of Washable hydrophilic silicone oil according to claim 3, it is characterized in that: under basic catalyst effect, hexamethyl cyclotrisiloxane changes hexamethyl dihydroxyl trisiloxanes into, by intermolecular dehydration, further polycondensation is low-molecular-weight end hydroxyl silicone oil, transesterification reaction is passed through again with piperizinylmethyl dimethoxysiloxane, change terminal hydroxy group amido silicon oil into, addition reaction is passed through again with both-end epoxy polyoxyethylene poly-oxygen propylene aether, change terminal hydroxy group amino-polyether silicone oil into, and then pass through nucleophilic substitution reaction with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, quaternary ammonium salt is connected on the secondary amino group in part piperazinyl, finally add difluoro dichloro pyrimidine, pass through nucleophilic substitution reaction, difluoro dichloro pyrimidine active group is connected on the secondary amino group in part piperazinyl, obtain block polyether quaternary ammonium salt silicone oil.
6. the preparation method of a kind of Washable hydrophilic silicone oil according to claim 3, it is characterized in that: under basic catalyst effect, octamethylcyclotetrasiloxane changes prestox dihydroxyl tetrasiloxane into, by intermolecular dehydration, further polycondensation is low-molecular-weight end hydroxyl silicone oil, transesterification reaction is passed through again with piperizinylmethyl dimethoxysiloxane, change terminal hydroxy group amido silicon oil into, addition reaction is passed through again with both-end epoxy polyoxyethylene poly-oxygen propylene aether, change terminal hydroxy group amino-polyether silicone oil into, and then pass through nucleophilic substitution reaction with 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, quaternary ammonium salt is connected on the secondary amino group in part piperazinyl, finally add difluoro dichloro pyrimidine, pass through nucleophilic substitution reaction, difluoro dichloro pyrimidine active group is connected on the secondary amino group in part piperazinyl, obtain block polyether quaternary ammonium salt silicone oil.
7. the preparation method of a kind of Washable hydrophilic silicone oil according to claim 4, is characterized in that: its concrete reactions steps is as follows:
1st step, drops into the terminal hydroxy group linear body silicone oil of 0.2mol, 0.85g potassium hydroxide, 0.04mol piperizinylmethyl dimethoxysiloxane, is warming up to 90-95 DEG C in reactor, reacts 3 hours;
2nd step, drop into 0.075mol both-end epoxy polyoxyethylene poly-oxygen propylene aether, 90-95 DEG C is continued reaction 3.5 hours;
3rd step, is cooled to 80-85 DEG C, drops into 0.008mol 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, reacts 3.5 hours;
4th step, is cooled to 40-45 DEG C, drops into 0.004mol difluoro dichloro pyrimidine, reacts 3 hours, namely obtain block polyether quaternary ammonium salt silicone oil.
8. the preparation method of a kind of Washable hydrophilic silicone oil according to claim 5, is characterized in that: the concrete reactions steps that its use hexamethyl cyclotrisiloxane prepares block polyether quaternary ammonium salt silicone oil is as follows:
1st step, drops into the hexamethyl cyclotrisiloxane of 0.5mol, 0.6mol deionized water, 1g potassium hydroxide, is warming up to 80-85 DEG C in reactor, reacts 0.5 hour;
2nd step, drops into 0.05mol piperizinylmethyl dimethoxysiloxane, is warming up to 120-125 DEG C, reacts 3.5 hours;
3rd step, is cooled to 85-90 DEG C, drops into 0.08mol both-end epoxy polyoxyethylene poly-oxygen propylene aether, continues reaction 3 hours,
4th step, is cooled to 80-85 DEG C, drops into 0.01mol 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, reacts 3 hours;
5th step, is cooled to 40-45 DEG C, drops into 0.005mol difluoro dichloro pyrimidine, reacts 3 hours, namely obtain block polyether quaternary ammonium salt silicone oil.
9. the preparation method of a kind of Washable hydrophilic silicone oil according to claim 6, is characterized in that: the concrete reactions steps that its use octamethylcyclotetrasiloxane prepares block polyether quaternary ammonium salt silicone oil is as follows:
1st step, drops into the octamethylcyclotetrasiloxane of 0.7mol, 0.85mol deionized water, 1g potassium hydroxide, is warming up to 80-85 DEG C in reactor, reacts 0.5 hour;
2nd step, drops into 0.075mol piperizinylmethyl dimethoxysiloxane, is warming up to 120-125 DEG C, reacts 3.5 hours;
3rd step, is cooled to 85-90 DEG C, drops into 0.12mol both-end epoxy polyoxyethylene poly-oxygen propylene aether, continues reaction 3 hours,
4th step, is cooled to 80-85 DEG C, drops into 0.015mol 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, reacts 3 hours;
5th step, is cooled to 40-55 DEG C, drops into 0.0065mol difluoro dichloro pyrimidine, reacts 3 hours, namely obtain block polyether quaternary ammonium salt silicone oil.
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| CN106637998B (en) * | 2016-10-18 | 2019-04-30 | 广东传化富联精细化工有限公司 | A kind of hydrophilic ice-feeling silicone oil and preparation method thereof |
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