CN102505496B - Aminosilicone durable hydrophilic potentiating agent, and preparation method and application thereof - Google Patents
Aminosilicone durable hydrophilic potentiating agent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses aminosilicone durable hydrophilic potentiating agent, and a preparation method and the application thereof. The preparation method is that methyl silicone oil containing hydrogen, allyl-terminated epoxy-terminated compound and allyl polyether are reacted under the effect of platinum catalyst in oxygen-free condition, so that the aminosilicone durable hydrophilic potentiating agent is obtained. The method has the advantages that the reaction step is simple, the reaction condition is mild, and the method is simple and easy. The aminosilicone durable hydrophilic potentiating agent not only can be independently used before and after the softening finish of traditional aminosilicone, but also can be co-bathed with traditional aminosilicone emulsion; as the agent has good penetrability, wettability and reactivity, the agent can not only keep the soft and smooth feel of the traditional aminosilicone, but also give good hydrophilicity to fabrics in the condition that the use level is low, and also has durability; and the difference between the fabric finished by the aminosilicone durable hydrophilic potentiating agent and the fabric finished by the independently used traditional traditional aminosilicone emulsion is that fabric treated by the aminosilicone durable hydrophilic potentiating agent can be directly repaired without treatment.
Description
Technical field
The invention belongs to technical field of textile chemical engineering, be specifically related to a kind of amido silicon oil (emulsion) durable hydrophilic potentiating agent and preparation method thereof and application.
Background technology
Amino-modified silicone oil in soft after-treating auxiliary, remains a kind of occupying dominant position at present in the history in existing more than 20 year of China's production application.Amido silicon oil can be widely used in the softening of various natural fibers and synthon, fabric through its arrangement has softness, smooth, the advantage such as plentiful and washable, traditional amido silicon oil can give fabric good feel, but also exist inborn deficiency, except in use, common amino silicon oil emulsion is worn the factors such as alkali or long-time shearing owing to cloth impact can occur outside breakdown of emulsion and the floating oil phenomenon, through the fabric after the common amino silicon oil emulsion arrangement, can be hydrophobicity and make the snugness of fit variation, and cause returning something for repairs at fabric, bad owing to permeating when redying, absorb inhomogeneous and serious look occurs and spend, therefore can't directly return something for repairs, must use special silicone oil stripper amido silicon oil thoroughly could be divested, then just can redye.Amido silicon oil is because hydrophilicity is poor in addition, and the fabric antistatic property after its arrangement is also poor, easily produces the caused variety of issue of static.Therefore, the hydrophilic modifying of common amido silicon oil becomes a focus of present silicone softening agent research, present stage the hydrophilic organic silicone softener mainly contain three classes, be respectively the amino block silicone oil of polyether modified silicon oil, hydrophilic polyether modified amino silicon oil and linear polyether.
The representative products of polyether modified silicon oil is the CGF of former Chenguang Chemical Inst., Ministry of Chemical Industry research and development, is characterized in good hydrophilic property, and feel is general, and washing fastness is relatively poor.The hydrophilic polyether modified amino silicon oil is to introduce simultaneously amino and hydrophilic polyether segment at the polysiloxane molecule side chain, so just can be under the prerequisite that to a certain degree keeps the amido silicon oil feel, improve the wetting ability of fabric, solved traditional amido silicon oil exist can not return something for repairs after dying, snugness of fit is poor and the problem of difficult cleaning.The problem of hydrophilic polyether modified amino silicon oil maximum is after wetting ability is better improved, feel is often comfortable not as the amino-modified silicone oil softness, vice versa, the relation of contradiction between the two, there is hydrophilic unabiding problem in this type of silicone oil such as the DC8600 of Dow Corning Corporation and the TEX180 of GE Toshiba in addition.Publication number is that the Chinese invention patent of CN 1919896A discloses a kind of method for preparing hydrophilic silicon oil, the method adopts silicon oil of low hydrogen content and polyethers to react under the effect of chain-transfer agent and catalyzer, introduce amino coupling agent, prepare at last amino modified hydrophilic silicon oil, the method has been improved the wetting ability of amido organosilicon softening agent, but the feel of the fabric of processing is declined to a great extent.And the amino block silicone oil of linear polyether is owing to being that straight-chain polyether amino is block modified, it pushes the hydrophilic organic silicon fabric finishing agent on the step of a renewal, well balance feel and hydrophilic contradiction, product is every to have good stability, very outstanding at aspects such as high temperature resistant, anti-high-shear, electrolyte-resistant and strong acid-base resistances, almost be fit to all rear finishing process.Publication number is the preparation method that the Chinese invention patent application of CN 101497967A discloses a kind of fabric softener block water-soluble silicon oil, the method adopts the amidation of amino coupling agent, preparation, the preparation of organopolysiloxane-polyethers linear block copolymers and four preparation processes of ammonia solution of segmented copolymer of the hydrogeneous methylsiloxane intermediate of end, the feel of common hydrophilic polyether modified amino silicon oil and the contradiction between the wetting ability have been improved, but complicated process of preparation, cost are very high.This series products is with the Magnasoft SRS of U.S. Mai Tu company, the extraordinary silicone oil such as Magnasoft JSS and MagnasoftSILQ are representative, domestic existing several companies and research institution are at this series products of exploitation, the cost of this type of hydrophilic organic silicone softener is very high, the several times of general amido silicon oil price, inapplicablely in common product, use, and with regard to the product that steps at present figure, selective to fabric during application, be particularly suitable for washing the soft rear arrangement of suede series products such as Magnasoft SRS, feel is good, and is hydrophilic relatively poor.
The present development of tradition amido silicon oil is very ripe, its style and feel are varied, comprise softness, smooth, fluffy and elasticity etc., its applicable scope has almost comprised all fabric types (cottons, hair, wash etc. and various BLENDED FABRIC), and it has very high cost performance, therefore, within long period of time, the tradition amido silicon oil still can be a softening agent kind of occupying dominant position, but people require more and more higher to the hydrophilic and snugness of fit of fabric, under these circumstances, seek the problem that a kind of amido silicon oil synergistic agent with good wetting ability and weather resistance becomes needs solution.
Summary of the invention
The object of the invention is to improve the wetting ability of traditional amido silicon oil, a kind of amido silicon oil (emulsion) durable hydrophilic potentiating agent and preparation method thereof is provided.
The structural formula of amido silicon oil provided by the present invention (emulsion) durable hydrophilic potentiating agent is suc as formula shown in the I:
(formula I)
Among the formula I, R is selected from any one in the following radicals :-CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH
2CH
2CH
2CH
3With-COCH
3
Integer between the a+b+c+d=1-20, a 〉=0 can not be 0 but b and d can not be 0, c and d simultaneously simultaneously;
N＞m 〉=0, the integer between the m+n=5-25;
Integer between the p+q=0-25, and be divided into following four kinds of situations: 1) when b=c=0 and d ≠ 0, q＞p 〉=0 and p+q=5-25; 2) when b=0 and c ≠ 0 and d ≠ 0, q＞p 〉=0 and p+q=5-25; 3) when b ≠ 0 and c=0 and d ≠ 0, p+q=0-25; 4) when b ≠ 0 and c ≠ 0 and d ≠ 0, p+q=0-25;
Be to comprise simultaneously the hydrophilic polyether segment in the molecular structure and have reactive epoxide group.
The method for preparing above-mentioned amido silicon oil (emulsion) durable hydrophilic potentiating agent comprises the steps: under the oxygen free condition, Methyl Hydrogen Polysiloxane Fluid and allylic cpd are reacted under the platinum catalyst effect, obtain described amido silicon oil (emulsion) durable hydrophilic potentiating agent.
Described method also is included in and vacuumizes underpressure distillation after reaction finishes and remove the small-molecule substance step of (comprising the low-molecular-weight component that do not react completely in Methyl Hydrogen Polysiloxane Fluid and the allylic cpd and the low boiling point solvent in the platinum catalyst).
Wherein, the structural formula of described Methyl Hydrogen Polysiloxane Fluid is (CH
3)
3SiO[(CH
3)
2SiO]
A[(CH
3) HSiO]
BSi (CH
3)
3, A 〉=0 wherein, B 〉=1 and A+B=1-20;
Described allylic cpd by following a)-d) in arbitrarily-the group material forms:
A) glycidyl allyl ether, the epoxy terminated compd A of end-allyl group and allyl polyether;
Wherein, the structural formula of described glycidyl allyl ether is CH
2=CHCH
2OCH
2(CHCH
2) O;
The structural formula of the epoxy terminated compd A of described end-allyl group is CH
2=CHCH
2O (C
3H
6O)
P(C
2H
4O)
QCH
2(CHCH
2) O, P 〉=0 wherein, the integer between Q 〉=0 and the P+Q=0-25;
The structural formula of described allyl polyether is CH
2=CHCH
2O (C
3H
6O)
m(C
2H
4O)
nR, n＞m 〉=0 wherein, the integer between the m+n=5-25, R is-CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH
2CH
2CH
2CH
3Or-COCH
3
B) the epoxy terminated compd A of described end-allyl group and described allyl polyether;
C) the epoxy terminated compd B of described glycidyl allyl ether and end-allyl group;
The structural formula of the epoxy terminated compd B of described end-allyl group is CH
2=CHCH
2O (C
3H
6O)
P(C
2H
4O)
QCH
2(CHCH
2) O, the wherein integer between Q＞P 〉=0 and the P+Q=5-25;
D) the epoxy terminated compd B of described end-allyl group.
Among the above-mentioned preparation method, the temperature of reaction of described reaction is 70-120 ℃, and the time is 1-12 hour.
Among the above-mentioned preparation method, the molar ratio of Si-H in the described Methyl Hydrogen Polysiloxane Fluid and the C=C in the allylic cpd (comprising the epoxy terminated compound of end-allyl group and allyl polyether) is 1.0: (1.0-5.0), and preferred 1.0: (1.1-1.6).
Used platinum catalyst specifically can be aqueous isopropanol and dimethyl siloxane and 1 of the dehydrated alcohol of platinum chloride or aqueous isopropanol, Platinic chloride, 3-divinyl-1,1,3, (dimethyl siloxane is as thinner or solvent for the mixture of 3-tetramethyl disiloxane platinum complex, main in order to make things convenient for the use of platinum catalyst) in a kind of, the consumption of platinum catalyst is counted the 10-100ppm of reactant total mass with platinum chloride, Platinic chloride or platinum complex, preferred 10-50ppm.
Among the above-mentioned preparation method, hydrophilic oxyethane segment (C
2H
4O) account for the ratio 20%-75% of preparation product total mass (by the selection of allylic cpd, comprise structure (ratio of EO and PO) and molecular weight, and the proportioning of conditioned reaction thing, main purpose is to regulate the hydrophilicity of synthetic product), and oxyethane segment (C
2H
4O) account for the massfraction of preparation product greater than propylene oxide segment (C
3H
6O); Has reactive epoxide group-(CHCH
2) the O ratio that accounts for preparation product total mass is 1%-10% (consumption, the structure of the epoxy terminated compound of end-allyl group and the proportioning of consumption and conditioned reaction thing etc. by the control glycidyl allyl ether realize, main purpose is the reactivity of control synthetic product).
In order to improve the wetting ability of traditional amido silicon oil, the invention provides a kind of amido silicon oil (emulsion) durable hydrophilic potentiating agent.This synergistic agent is introduced hydrophilic segment (hydrophilic polyether segment) and reactive group (epoxide group) simultaneously in molecular structure, both cooperated and before or after traditional amido silicon oil softening, to use separately with amido silicon oil (emulsion), also can use with bathing with traditional amino silicon oil emulsion.In the situation that consumption seldom, both can keep the soft and smooth feel of traditional amido silicon oil fully, can give again fabric fabulous wetting ability, and have weather resistance.Be different from the fabric after simple traditional amido silicon oil is put in order, can directly return something for repairs without processing through the fabric after the durable hydrophilic potentiating agent arrangement.
Amido silicon oil provided by the present invention (emulsion) durable hydrophilic potentiating agent can be used for textile finishing.
A further object of the present invention provides a kind of method that fabric is put in order.
When fabric was put in order, amido silicon oil hydrophilic potentiating agent of the present invention can use before or after traditional amido silicon oil softening separately, perhaps used with bathing with traditional amino silicon oil emulsion; Should fully dissolve and mix before using.
Specifically comprise the steps: to adopt amido silicon oil provided by the invention (emulsion) durable hydrophilic potentiating agent by the method for rolling of soaking fabric to be put in order.
The condition that described one method of rolling of soaking is put in order fabric is: fabric one soaks one and rolls working fluid, and pressure is 2-5Kg/cm
2, mangle expression 70-75%; Bake 60-120s under drying 60-120s, 140-160 ℃ under 90-110 ℃;
Described working fluid is: the 1) aqueous solution of described amido silicon oil hydrophilic potentiating agent, or 2) mixed aqueous solution of amido silicon oil and described amido silicon oil hydrophilic potentiating agent; The mass concentration of amido silicon oil hydrophilic potentiating agent is 0.05-10% in the described working fluid.
When described working fluid was the aqueous solution of described amido silicon oil hydrophilic potentiating agent, described method also comprised following 1) or 2): 1) described fabric is carried out the step of pre-treatment with amido silicon oil; The step of 2) fabric after the described method processing being carried out aftertreatment with amido silicon oil.
Above-mentioned amido silicon oil comprises the amino block silicone oil of traditional amido silicon oil (as spinning chemical inc FK-220C32, FK-220D19, FK-220C33 in Beijing) and polyether modified silicon oil, hydrophilic polyether modified amino silicon oil (as spinning chemical inc FK-220F5 in Beijing) and linear polyether (as spinning chemical inc FK-220F8 in Beijing) etc.
The present invention compared with prior art has following advantage:
1, preparation feedback mild condition, reaction process is simple.
2, good stability, consumption is few, and cost is low, and is applied widely, and application art is simple to operation, both can separately in the forward and backward use of amido silicon oil softening, also can use with bathing with amino silicon oil emulsion.
3, can give fabric fabulous wetting ability, and not affect the feel of amido silicon oil fully, remedy the defective of traditional amido silicon oil hydrophilicity aspect, the fabric after its arrangement can be redyed without processing directly to return something for repairs.
4, after its arrangement, to do the time spent with fabric and be combined more firmly with the form of chemical bond, the wetting ability of fabric has weather resistance.
Description of drawings
Fig. 1 is the infrared spectrum of amido silicon oil (emulsion) durable hydrophilic potentiating agent of embodiment 1 preparation.
Fig. 2 is the infrared spectrum of amido silicon oil (emulsion) durable hydrophilic potentiating agent of embodiment 2 preparations.
Fig. 3 is the infrared spectrum of amido silicon oil (emulsion) durable hydrophilic potentiating agent of embodiment 3 preparations.
Fig. 4 is the infrared spectrum of amido silicon oil (emulsion) durable hydrophilic potentiating agent of embodiment 4 preparations.
Fig. 5 is the infrared spectrum of amido silicon oil (emulsion) durable hydrophilic potentiating agent of embodiment 5 preparations.
Embodiment
The present invention will be described below by specific embodiment, but the present invention is not limited thereto.
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
Among the following embodiment the wetting ability testing method of using and feel testing method and standard as follows:
Wetting ability test: AATCC-79 method: cloth specimen (in air moisture regain one night) entirely is fixed on the cloth circle that stretches tight, and is the drop-burette of 1mm with the titration nozzle diameter, is being the 1cm place water that drips from the cloth cover height, and is beginning timing.When globule when reflectance is reduced to a complete opaque watermark gradually, stop timing, to test 3-5 point and average, the complete diffusion time of water droplet is shorter, illustrates that hydrophilicity is better.
The feel test: the evaluation of hand digital palpation for examination of trauma, 5 people form a group, finish fabric is touched, and grade.Feel is divided into 5 grades, and take unfinished blank cloth as 1 grade, the grade regulation of the best is 5 grades, and other fabric is graded with respect to this standard.
1. amido silicon oil (emulsion) durable hydrophilic potentiating agent is synthetic
The mixture of the allyl polyether of the end-allyl group polyoxy alkyl epoxy base ether of 79.0g Methyl Hydrogen Polysiloxane Fluid, 17.1g glycidyl allyl ether, 322.8g and 414g is dropped in the reactor, logical nitrogen is also opened and is stirred, be warming up to 85 ℃, aqueous isopropanol (mass concentration 10%) 0.238g that adds Platinic chloride, the consumption of catalyzer (in Platinic chloride) is according to the 30ppm of reactant total mass (namely 3 * 10
-5) add, insulation reaction 5 hours, then low-volatile material is sloughed in underpressure distillation, and the transparent liquid that obtains is amido silicon oil (emulsion) durable hydrophilic potentiating agent, and its solid content is at least 99%.
R is-CH among the formula I
3, a=2, b=3, c=1, d=4, m=4, n=14, p=2, q=7;
The Methyl Hydrogen Polysiloxane Fluid structural formula is (CH
3)
3SiO[(CH
3)
2SiO]
2[(CH
3) HSiO]
8Si (CH
3)
3
The glycidyl allyl ether structural formula is CH
2=CHCH
2OCH
2(CHCH
2) O
End-allyl group polyoxy alkyl epoxy base ether structure formula is CH
2=CHCH
2O (C
3H
6O)
2(C
2H
4O)
7CH
2(CHCH
2) O
The structural formula of allyl polyether is CH
2=CHCH
2O (C
3H
6O)
4(C
2H
4O)
14CH
3
The infrared spectrum of synthetic product is seen Fig. 1.As shown in Figure 1,3050cm
-1For the stretching vibration peak of C-H in the epoxy group(ing), at 2970～2887cm
-1The place is in the polymkeric substance-CH
3With-CH
2The absorption peak of-group, 1640～1660cm
-1Be the charateristic avsorption band of C=C key in the excessive allylic cpd, 1255cm
-1Si-CH
3In-CH
3The symmetrical deformation vibration absorption peak, 1130～1000cm
-1The place is the overlapping peaks of C-O-C stretching vibration and Si-O-Si stretching vibration absorption peak, 803cm
-1Near be Si-CH
3The stretching vibration absorption peak of middle Si-C, 1450cm
-1The flexural vibration absorption peak of saturated c h bond, at 2280～2080cm
-1Do not have the charateristic avsorption band of Si-H to occur, this shows that Si-H disappears substantially, and infrared spectrum can be verified and synthesize target product.
2. textile finishing and performance test
In deionized water, add 0.2% above-mentioned durable hydrophilic potentiating agent, be mixed with working fluid (padding liquid) after fully mixing, soak a technique of rolling to putting in order through the black plain weave pure cotton woven fabric after traditional amino silicon oil emulsion mellowing by one, find that the cotton fabric infiltration osmotic effect after working fluid is to traditional amino silicon oil emulsion softening is good, pressure is 3Kg/cm
2, mangle expression is 75%; Then fabric is dried 90s at 100 ℃, 140 ℃ bake 120s.
5 professionals adopt the feel of hand digital palpation for examination of trauma evaluation fabric, and wetting ability adopts the water droplet osmose process to measure according to the AATCC-79 method.Test result is as follows:
Table 1 feel and wetting ability test result
The textile woven fabric of black plain weave, in spin plain reactive black G, consumption 3%o.w.f.; Tradition amido silicon oil (spinning chemical inc FK-220C32 in Beijing) and hydrophilic polyether modified amino silicon oil (spinning chemical inc FK-220F5 in Beijing) are the commercial goods.
Table 2 returns something for repairs and redyes the result
| Cloth specimen (the textile woven fabric of black plain weave) | Outward appearance | Standard deviation value | The K/S value |
| After the arrangement of tradition amido silicon oil (before returning something for repairs) | Evenly, colourless flower | 0.21 | 8.2 |
| After the arrangement of tradition amido silicon oil (after returning something for repairs) | Obvious look flower is arranged | 0.95 | 9.4 |
| Through after |
Evenly, colourless flower | 0.23 | 12.6 |
(dyestuff of redying usefulness of returning something for repairs spins plain reactive black G, consumption 2.5%o.w.f., bath raio 1: 20 in being; Measure case depth K/S value and standard deviation value with U.S. Datacolor Computer color testing color matching instrument, the K/S value is larger, illustrates that the cloth specimen color is darker; The K/S value is less, and color is more shallow; Standard deviation value is larger, illustrates that the cloth specimen color is more inhomogeneous, and standard deviation value is less, and account for color is more even)
Embodiment 2
1. amido silicon oil (emulsion) durable hydrophilic potentiating agent is synthetic
The mixture of the allyl polyether of the glycidyl allyl ether of the Methyl Hydrogen Polysiloxane Fluid of 41.6g, 27.4g and 50.6g is dropped in the reactor, logical nitrogen is also opened and is stirred, be warming up to 95 ℃, ethanol solution (mass concentration 12%) 0.05g that adds platinum chloride, the consumption of catalyzer (in platinum chloride) is according to the 50ppm of reactant total mass (namely 5 * 10
-5) add, insulation reaction 7 hours, then low-volatile material is sloughed in underpressure distillation, and the transparent liquid that obtains is amido silicon oil (emulsion) durable hydrophilic potentiating agent, and its solid content is at least 98%.
R is-CH among the formula I
2CH
2CH
2CH
3, a=2, b=1, c=2, d=0, n=7, m=0;
The Methyl Hydrogen Polysiloxane Fluid structural formula is (CH
3)
3SiO[(CH
3)
2SiO] [(CH
3) HSiO]
3Si (CH
3)
3
The glycidyl allyl ether structural formula is CH
2=CHCH
2OCH
2(CHCH
2) O
The structural formula of allyl polyether is CH
2=CHCH
2O (C
2H
4O)
7CH
2CH
2CH
2CH
3
The infrared spectrum of synthetic product is seen Fig. 2.As shown in Figure 2, synthetic product is target product.
2. textile finishing and performance test
First traditional amino silicon oil emulsion of 20% is made into the working fluid of 40g/L, then in this working fluid, add 0.1% above-mentioned durable hydrophilic potentiating agent, after fully mixing, soak a technique of rolling by one the textile woven fabric of blueness is carried out softening, pressure is 2.7Kg/cm
2, then mangle expression 75% dries 100 ℃ * 120s, bakes 140 ℃ * 120s.5 professionals adopt the feel of hand digital palpation for examination of trauma evaluation fabric, and wetting ability adopts the water droplet osmose process to measure according to the AATCC-79 method.The result is as follows:
Table 3 feel and wetting ability test result
| Sample | Feel | Wetting ability/s | Wash the wetting ability/s after 5 times |
| Blank (being untreated) | 1 grade | 0.8s | 0.8s |
| The tradition amido silicon oil | 5 grades | ＞120s, not hydrophilic | ＞120s, not hydrophilic |
| The amino block silicone oil of linear polyether | 4.5 level | 3.5s | 3.5s |
| Embodiment 2 | 5 grades | 0.9s | 0.8s |
Blue textile woven fabric; The amino block silicone oil of tradition amido silicon oil (spinning chemical inc FK-220D19 in Beijing) and linear polyether (spinning chemical inc FK-220F8 in Beijing) is the commercial goods.
Embodiment 3
1. amido silicon oil (emulsion) durable hydrophilic potentiating agent is synthetic
The mixture of the allyl polyether of the end-allyl group polyoxy alkyl epoxy base ether of the Methyl Hydrogen Polysiloxane Fluid of 80.4g, 448.8g and 335g is dropped in the reactor, logical nitrogen is also opened and is stirred, be warming up to 92 ℃, add 1 in the dimethyl siloxane, 3-divinyl-1,1,3,3-tetramethyl disiloxane platinum complex (mass concentration 15%) 0.086g, the consumption of catalyzer is (with 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum complex meter) according to the 15ppm of reactant total mass (namely 1.5 * 10
-5) add, insulation reaction 6 hours, then low-volatile material is sloughed in underpressure distillation, and the transparent liquid that obtains is amido silicon oil (emulsion) durable hydrophilic potentiating agent, and its solid content is at least 99%.
R is-COCH among the formula I
3, a=3, b=4, c=0, d=3, m=3, n=9, p=6, q=15;
The Methyl Hydrogen Polysiloxane Fluid structural formula is (CH
3)
3SiO[(CH
3)
2SiO]
3[(CH
3) HSiO]
7Si (CH
3)
3
End-allyl group polyoxy alkyl epoxy base ether structure formula is CH
2=CHCH
2O (C
3H
6O)
6(C
2H
4O)
15CH
2(CHCH
2) O
The structural formula of allyl polyether is CH
2=CHCH
2O (C
3H
6O)
3(C
2H
4O)
9COCH
3
The infrared spectrum of synthetic product is seen Fig. 3.As shown in Figure 3, synthetic product is target product.
2. textile finishing and performance test
First traditional amino silicon oil emulsion of 25% is made into the working fluid of 40g/L, then in this working fluid, add 0.3% above-mentioned durable hydrophilic potentiating agent, after fully mixing, soak a technique of rolling by one red pure cotton knitting cloth is carried out softening, pressure is 3.5Kg/cm
2, then mangle expression 75% dries 110 ℃ * 90s, bakes 140 ℃ * 90s, and 5 professionals adopt the feel of hand digital palpation for examination of trauma evaluation fabric, and wetting ability adopts the water droplet osmose process to measure according to the AATCC-79 method.The result is as follows:
Table 4 feel and wetting ability test result
| Sample | Feel | Wetting ability/s | Wash the wetting ability/s after 5 times |
| Blank (being untreated) | 1 grade | 1.2s | 1.2s |
| The tradition amido silicon oil | 5 grades | ＞120s, not hydrophilic | ＞120s, not hydrophilic |
| The hydrophilic polyether modified amino silicon oil | 4 grades | 5.3s | 5.3s |
| The amino block silicone oil of linear polyether | 4.5 level | 2.1s | 2.1s |
| Embodiment 3 | 5 grades | 1.5s | 1.6s |
Red pure cotton knitting cloth, in spin plain reactive red 3BS, 3%o.w.f.; Tradition amido silicon oil (spinning chemical inc FK-220C33 in Beijing), hydrophilic polyether modified amino silicon oil (spinning chemical inc FK-220F5 in Beijing) and the amino block silicone oil of linear polyether (spinning chemical inc FK-220F8 in Beijing) are the commercial goods.
Table 5 returns something for repairs and redyes the result
| Cloth specimen (red pure cotton knitting cloth) | Outward appearance | Standard deviation value | The K/S value |
| Original cloth specimen (after returning something for repairs) | Evenly, colourless flower | 0.14 | 14.8 |
| After the arrangement of tradition amido silicon oil (after returning something for repairs) | Obvious look flower is arranged | 0.75 | 10.2 |
| Through embodiment 3 arrangements (after returning something for repairs) | Evenly, colourless flower | 0.17 | 14.9 |
(dyestuff of redying usefulness of returning something for repairs spins plain reactive red 3BS, consumption 1%o.w.f., bath raio 1: 20 in being; Measure case depth K/S value and standard deviation value with U.S. Datacolor Computer color testing color matching instrument, the K/S value is larger, illustrates that the cloth specimen color is darker; The K/S value is less, and color is more shallow; Standard deviation value is larger, illustrates that the cloth specimen color is more inhomogeneous, and standard deviation value is less, and account for color is more even)
Embodiment 4
1. amido silicon oil (emulsion) durable hydrophilic potentiating agent is synthetic
The mixture of the end-allyl group polyoxy alkyl epoxy base ether of the glycidyl allyl ether of the Methyl Hydrogen Polysiloxane Fluid of 91g, 37.6g and 639.1g is dropped in the reactor, logical nitrogen is also opened and is stirred, be warming up to 90 ℃, aqueous isopropanol (concentration 18%) 0.107g that adds Platinic chloride, the consumption of catalyzer (in Platinic chloride) is according to the 25ppm of reactant total mass (namely 2.5 * 10
-5) add, insulation reaction 5 hours, then low-volatile material is sloughed in underpressure distillation, and the transparent liquid that obtains is amido silicon oil (emulsion) durable hydrophilic potentiating agent, and its solid content is at least 98%.
A=2 among the formula I, b=0, c=3, d=7, p=4, q=11;
The Methyl Hydrogen Polysiloxane Fluid structural formula is (CH
3)
3SiO[(CH
3)
2SiO]
2[(CH
3) HSiO]
10Si (CH
3)
3
The glycidyl allyl ether structural formula is CH
2=CHCH
2OCH
2(CHCH
2) O
End-allyl group polyoxy alkyl epoxy base ether structure formula is CH
2=CHCH
2O (C
3H
6O)
4(C
2H
4O)
11CH
2(CHCH
2) O
The infrared spectrum of synthetic product is seen Fig. 4.As shown in Figure 4, synthetic product is target product.
2. textile finishing and performance test
In deionized water, add 0.25% above-mentioned durable hydrophilic potentiating agent, be mixed with working fluid after fully mixing, soaking a technique of rolling by one puts in order white polyester-cotton blend woven fabric thing, after the process oven dry bakes, again traditional amino silicon oil emulsion of 20% is made into the working fluid of 30g/L, then soak the polyester-cotton fabric of a technique of rolling after to above-mentioned arrangement with this working fluid by one and carry out softening, pressure is 3Kg/cm
2, mangle expression 71%, 95 ℃ * 120s of oven dry bakes 150 ℃ * 90s.5 professionals adopt the feel of hand digital palpation for examination of trauma evaluation fabric, and wetting ability adopts the water droplet osmose process to measure according to the AATCC-79 method.The result is as follows:
Table 6 feel and wetting ability test result
| Sample | Feel | Wetting ability/s | Wash the wetting ability/s after 5 times |
| Blank (being untreated) | 1 grade | ＞120s, not hydrophilic | ＞120s, not hydrophilic |
| The tradition amido silicon oil | 5 grades | ＞120s, not hydrophilic | ＞120s, not hydrophilic |
| The hydrophilic polyether modified amino silicon oil | 3.5 level | 10.4s | 10.2s |
| The amino block silicone oil of linear polyether | 4 grades | 30.1s | 30.3s |
| Embodiment 4 | 5 grades | 1.3s | 1.3s |
White twill polyester-cotton blend woven fabric; Tradition amido silicon oil (spinning chemical inc FK-220D19 in Beijing), hydrophilic polyether modified amino silicon oil (spinning chemical inc FK-220F5 in Beijing) and the amino block silicone oil of linear polyether (spinning chemical inc FK-220F8 in Beijing) are the commercial goods.
Embodiment 5
1. amido silicon oil (emulsion) durable hydrophilic potentiating agent is synthetic
The mixture of the end-allyl group polyoxy alkyl epoxy base ether of the Methyl Hydrogen Polysiloxane Fluid of 44.4g and 150.6g is dropped in the reactor, logical nitrogen is also opened and is stirred, be warming up to 90 ℃, add 1 in the dimethyl siloxane, 3-divinyl-1,1,3,3-tetramethyl disiloxane platinum complex (mass concentration 12%) 0.016g, the consumption of catalyzer is (with 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum complex meter) 10ppm according to the reactant total mass adds, insulation reaction 8 hours, and then low-volatile material is sloughed in underpressure distillation, the transparent liquid that obtains is amido silicon oil (emulsion) durable hydrophilic potentiating agent, and its solid content is at least 99%.
A=b=c=0 among the formula I, d=1, p=6, q=15;
The Methyl Hydrogen Polysiloxane Fluid structural formula is (CH
3)
3SiO[(CH
3) HSiO] Si (CH
3)
3
End-allyl group polyoxy alkyl epoxy base ether structure formula is CH
2=CHCH
2O (C
3H
6O)
2(C
2H
4O)
7CH
2(CHCH
2) O
The infrared spectrum of synthetic product is seen Fig. 5.As shown in Figure 5, synthetic product is target product.
2. textile finishing and performance test
First traditional amino silicon oil emulsion of 20% is made into the working fluid of 30g/L, then in this working fluid, add 0.4% above-mentioned durable hydrophilic potentiating agent, after fully mixing, soak a technique of rolling by one green terylene woven fabric is carried out softening, pressure is 3.3Kg/cm
2, then mangle expression 73% dries 105 ℃ * 60s, bakes 160 ℃ * 90s.5 professionals adopt the feel of hand digital palpation for examination of trauma evaluation fabric, and wetting ability adopts the water droplet osmose process to measure according to the AATCC-79 method.The result is as follows:
Table 7 feel and wetting ability test result
| Sample | Feel | Wetting ability/s | Wash the wetting ability/s after 5 times |
| Blank (being untreated) | 1 grade | ＞120s, not hydrophilic | ＞120s, not hydrophilic |
| The tradition amido silicon oil | 5 grades | ＞120s, not hydrophilic | ＞120s, not hydrophilic |
| The hydrophilic polyether modified amino silicon oil | 4 grades | 21.3s | 21.6s |
| The amino block silicone oil of linear polyether | 5 grades | 44.1s | 43.5s |
| Embodiment 5 | 5 grades | 2.7s | 2.9s |
Green terylene woven fabric; Tradition amido silicon oil (spinning chemical inc FK-220D19 in Beijing), hydrophilic polyether modified amino silicon oil (spinning chemical inc FK-220F5 in Beijing) and the amino block silicone oil of linear polyether (spinning chemical inc FK-220F8 in Beijing) are the commercial goods.
Claims (12)
1. the amido silicon oil hydrophilic potentiating agent shown in the formula I:
(formula I)
In the formula I, R is selected from any one in the following radicals :-CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH
2CH
2CH
2CH
3With-COCH
3
Integer between a+b+c+d=1-20, a 〉=0, and b and d can not be that 0, c and d can not be 0 simultaneously simultaneously;
N＞m 〉=0, the integer between the m+n=5-25;
Integer between the p+q=0-25, and minute following situation to p q limit: 1) when b=c=0 and the d ≠ 0, q＞p 〉=0 and p+q=5-25; 2) when b=0 and c ≠ 0 and d ≠ 0, q＞p 〉=0 and p+q=5-25; 3) when b ≠ 0 and c=0 and d ≠ 0, p+q=0-25; 4) when b ≠ 0 and c ≠ 0 and d ≠ 0, p+q=0-25.
2. method for preparing amido silicon oil hydrophilic potentiating agent shown in the claim 1 Chinese style I, comprise the steps: under the oxygen free condition, Methyl Hydrogen Polysiloxane Fluid and allylic cpd are reacted under the platinum catalyst effect, obtain described amido silicon oil hydrophilic potentiating agent;
Wherein, the structural formula of described Methyl Hydrogen Polysiloxane Fluid is (CH
3)
3SiO[(CH
3)
2SiO]
A[(CH
3) HSiO]
BSi (CH
3)
3, A 〉=0 wherein, the integer between B 〉=1 and the A+B=1-20;
Described allylic cpd by following a)-d) in any one group of material form:
A) glycidyl allyl ether, the epoxy terminated compd A of end-allyl group and allyl polyether;
Wherein, the structural formula of described glycidyl allyl ether is CH
2﹦ CHCH
2OCH
2(CHCH
2) O;
The structural formula of the epoxy terminated compd A of described end-allyl group is CH
2﹦ CHCH
2O(C
3H
6O)
P(C
2H
4O)
QCH
2(CHCH
2) O, P 〉=0 wherein, the integer between Q 〉=0 and the P+Q=0-25;
The structural formula of described allyl polyether is CH
2﹦ CHCH
2O(C
3H
6O)
m(C
2H
4O)
nR, n＞m 〉=0 wherein, the integer between the m+n=5-25, R is-CH
3,-CH
2CH
3,-CH
2CH
2CH
2CH
3Or-COCH
3
B) the epoxy terminated compd A of described end-allyl group and described allyl polyether;
C) the epoxy terminated compd B of described glycidyl allyl ether and end-allyl group;
The structural formula of the epoxy terminated compd B of described end-allyl group is CH
2﹦ CHCH
2O(C
3H
6O)
P(C
2H
4O)
QCH
2(CHCH
2) O, the wherein integer between Q＞P 〉=0 and the P+Q=5-25;
D) the epoxy terminated compd B of described end-allyl group.
3. method according to claim 2, it is characterized in that: the temperature of reaction of described reaction is 70-120 ℃, the time is 1-12 hour;
In the described reaction, the Si-H in the described Methyl Hydrogen Polysiloxane Fluid and the molar ratio of the C=C in the allylic cpd are 1.0:(1.0-5.0).
4. method according to claim 3, it is characterized in that: in the described reaction, the Si-H in the described Methyl Hydrogen Polysiloxane Fluid and the molar ratio of the C=C in the allylic cpd are 1.0:(1.1-1.6).
5. each described method according to claim 2-4, it is characterized in that: described platinum catalyst is aqueous isopropanol and dimethyl siloxane and 1 of the dehydrated alcohol of platinum chloride or aqueous isopropanol, Platinic chloride, 3-divinyl-1,1, in the mixture of 3,3-tetramethyl disiloxane platinum complex any one; The consumption of described platinum catalyst is counted the 10-100ppm of reactant total mass with platinum chloride, Platinic chloride or platinum complex.
6. method according to claim 5, it is characterized in that: the consumption of described platinum catalyst is counted the 10-50ppm of reactant total mass with platinum chloride, Platinic chloride or platinum complex.
7. method according to claim 2 is characterized in that: among the described preparation method, and hydrophilic oxyethane segment C
2H
4The ratio that O accounts for preparation product total mass is 20%-75%, and oxyethane segment C
2H
4O accounts for the massfraction of preparation product greater than propylene oxide segment C
3H
6O; Has reactive epoxide group-(CHCH
2) the O ratio that accounts for preparation product total mass is 1%-10%.
8. method according to claim 2 is characterized in that: described method also is included in the step that vacuumizes underpressure distillation after reaction finishes.
9. the application of the described amido silicon oil hydrophilic potentiating agent of claim 1 in textile finishing.
10. the method that fabric is put in order comprises the steps: to adopt the described amido silicon oil hydrophilic potentiating agent of claim 1 by the method for rolling of soaking fabric to be put in order.
11. method according to claim 10 is characterized in that: the condition that described one method of rolling of soaking is put in order fabric is: fabric one soaks one and rolls working fluid, and pressure is 2-5Kg/cm
2, mangle expression 70-75%; Bake 60-120s under drying 60-120s, 140-160 ℃ under 90-110 ℃;
Wherein, described working fluid is: the 1) aqueous solution of described amido silicon oil hydrophilic potentiating agent, or 2) mixed aqueous solution of amido silicon oil and described amido silicon oil hydrophilic potentiating agent; The mass concentration of amido silicon oil hydrophilic potentiating agent is 0.05-10% in the described working fluid.
12. method according to claim 11 is characterized in that: described working fluid is the aqueous solution of described amido silicon oil hydrophilic potentiating agent, and described method also comprises following 1) and/or 2):
1) described fabric is carried out the step of pre-treatment with amido silicon oil;
The step of 2) fabric after the described method processing being carried out aftertreatment with amido silicon oil.
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| EP3262104B1 (en) * | 2015-02-28 | 2019-06-19 | Evonik Degussa GmbH | Oem textile finishing compositions |
| CN107964100A (en) * | 2016-10-19 | 2018-04-27 | 苏州汉力新材料有限公司 | A kind of preparation method of epoxy modified polysiloxane |
| CN107226909A (en) * | 2017-07-31 | 2017-10-03 | 王金桢 | A kind of fabric softener epoxy modified polysiloxane preparation method processed |
| CN108914593A (en) * | 2018-07-27 | 2018-11-30 | 浙江同辉纺织股份有限公司 | A kind of processing technology of cool fabric |
| CN110983787B (en) * | 2019-12-17 | 2022-02-11 | 广东新翔星科技股份有限公司 | Hydrophilic thickening organosilicon softening agent and preparation method thereof |
| CN111944094B (en) * | 2020-08-07 | 2022-01-07 | 西南石油大学 | Hydrogel copolymer, oil-water separation coating, preparation method and application of oil-water separation coating, oil-water separation net and preparation method of oil-water separation net |
| CN117306263B (en) * | 2023-10-18 | 2024-04-30 | 广州蓝博纺织品有限公司 | Far infrared anion antibacterial multifunctional health quilt and preparation method thereof |
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