CN102505496A - 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 hydrophilic synergist of a kind of amido silicon oil (emulsion) durability and preparation method thereof and application.
Background technology
Amino-modified silicone oil in soft after-treating auxiliary, remains a kind of occupying leading 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 soft finish of various natural fabrics and synthetic fiber; Have softness, advantage such as smooth, plentiful and washable through the fabric of its arrangement, traditional amido silicon oil can give fabric good feel, but also exists inborn deficiency; Except in use; Common amino silicon oil emulsion is because cloth is worn the influence of factors such as alkali or long-time shearings can occur outside breakdown of emulsion and the floating oil phenomenon, and the fabric after the common amino silicon oil emulsion of process is put in order can be hydrophobicity and makes the snugness of fit variation; And cause returning something for repairs at lining, bad when redying owing to infiltration, absorb the inhomogeneous serious look flower that occurs; Therefore can't directly return something for repairs, must use special silicone oil stripper could amido silicon oil thoroughly be divested, just can redye then.Amido silicon oil is because hydrophilicity is poor in addition, and the fabric antistatic property after its arrangement is also poor, is easy to generate 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 types, 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 washability is relatively poor.The hydrophilic polyether modified amino silicon oil is to introduce amino and hydrophilic polyether segment simultaneously 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 hydrophily of fabric, solved traditional amido silicon oil exist can not return something for repairs after dying, snugness of fit difference and difficult problem of cleaning.The maximum problem of hydrophilic polyether modified amino silicon oil is after hydrophily is better improved; Feel is often comfortable not as the amino-modified silicone oil softness; Vice versa; Be the relation of contradiction between the two, there is hydrophilic unabiding problem in this type of silicone oil like 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; This method adopts silicon oil of low hydrogen content and polyethers under the effect of chain-transferring agent and catalyst, to react; Introduce amino coupling agent; Prepare amino modified hydrophilic silicon oil at last, this method has been improved the hydrophily of amido organosilicon softener, but the feel of the fabric of handling is declined to a great extent.And the amino block silicone oil of linear polyether is owing to be 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 each item has good stability, and is very outstanding at aspects such as high temperature resistant, anti-high shear, electrolyte-resistant and strong acid-base resistances, almost is fit to all back 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; This method adopts the amidatioon of amino coupling agent, preparation, the polysiloxane-preparation of polyethers linear block copolymers and the ammonia of block copolymer of the hydrogeneous methylsiloxane intermediate of end to separate four preparation processes; The feel of common hydrophilic polyether modified amino silicon oil and the contradiction between the hydrophily 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, and extraordinary silicone oil such as Magnasoft JSS and MagnasoftSILQ are representative, and 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; Be the several times of general amido silicon oil price, inapplicablely in common product, use, and with regard to the product that steps figure at present; Selective during application to fabric; Such as the soft back arrangement that Magnasoft SRS is particularly suitable for washing the suede series products, feel is good, and is hydrophilic relatively poor.
The present development of tradition amido silicon oil is very ripe, and its style and feel are varied, comprises softness, smooth, fluffy and elasticity etc.; Its applicable scope has almost comprised all fabric types (cotton, hair, wash etc. and various BLENDED FABRIC); And it has very high cost performance, therefore, and in long period of time; The tradition amido silicon oil still can be a softener kind of occupying leading position; But people are increasingly high to the hydrophilic and snugness of fit requirement of fabric, under these circumstances, seek the problem that a kind of amido silicon oil synergist with good hydrophily and durability becomes needs solution.
Summary of the invention
The objective of the invention is to improve the hydrophily of traditional amido silicon oil, hydrophilic synergist of a kind of amido silicon oil (emulsion) durability and preparation method thereof is provided.
The structural formula of the hydrophilic synergist of amido silicon oil provided by the present invention (emulsion) durability 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, but b and d can not be 0 simultaneously, c and d can not be 0 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 situation: 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 the hydrophilic polyether segment in the molecular structure simultaneously and have reactive epoxide group.
The method for preparing the hydrophilic synergist of above-mentioned amido silicon oil (emulsion) durability comprises the steps: under the oxygen free condition; Methyl Hydrogen Polysiloxane Fluid and allyl compound are reacted under the platinum catalyst effect, obtain the hydrophilic synergist of said amido silicon oil (emulsion) durability.
Said method also is included in and vacuumizes decompression 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 allyl compound and the low boiling point solvent in the platinum catalyst).
Wherein, the structural formula of said 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;
Said allyl compound by following a)-d) in arbitrarily-the group material forms:
A) allyl glycidyl ether, end allyl end ring oxo-compound A and allyl polyether;
Wherein, the structural formula of said allyl glycidyl ether is CH
2=CHCH
2OCH
2(CHCH
2) O;
The structural formula of said end allyl end ring oxo-compound A 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 said 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) said end allyl end ring oxo-compound A and said allyl polyether;
C) said allyl glycidyl ether and end allyl end ring oxo-compound B;
The structural formula of said end allyl end ring oxo-compound B 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) said end allyl end ring oxo-compound B.
Among the above-mentioned preparation method, the reaction temperature of said reaction is 70-120 ℃, and the time is 1-12 hour.
Among the above-mentioned preparation method, the amount of substance ratio of Si-H in the said Methyl Hydrogen Polysiloxane Fluid and the C=C in the allyl compound (comprising end allyl end ring oxo-compound and allyl polyether) is 1.0: (1.0-5.0), and preferred 1.0: (1.1-1.6).
Used platinum catalyst specifically can be absolute ethyl alcohol or the aqueous isopropanol of platinum chloride, aqueous isopropanol and dimethyl siloxane and 1 of chloroplatinic acid; 3-divinyl-1,1,3; (dimethyl siloxane is as diluent or solvent for the mixture of 3-tetramethyl disiloxane platinum complex; The main use of platinum catalyst for ease) a kind of in, the consumption of platinum catalyst is counted the 10-100ppm of reactant gross mass, preferred 10-50ppm with platinum chloride, chloroplatinic acid or platinum complex.
Among the above-mentioned preparation method, hydrophilic oxirane segment (C
2H
4O) the ratio 20%-75% that accounts for preparation product gross mass is (through the selection of allyl compound; 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 oxirane segment (C
2H
4O) mass fraction that accounts for the preparation product is greater than expoxy propane segment (C
3H
6O); Has reactive epoxide group-(CHCH
2) the O ratio that accounts for preparation product gross mass is 1%-10% (proportioning of the consumption through the control allyl glycidyl ether, the structure of end allyl end ring oxo-compound and consumption and conditioned reaction thing waits and realizes that main purpose is the reactivity of control synthetic product).
In order to improve the hydrophily of traditional amido silicon oil, the invention provides the hydrophilic synergist of a kind of amido silicon oil (emulsion) durability.This synergist 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 soft finish, to use separately with amido silicon oil (emulsion), also can use with bathing with traditional amino silicon oil emulsion.Under the situation of consumption seldom, both can keep traditional amido silicon oil softness and smooth hand feeling fully, can give fabric fabulous hydrophily again, and have durability.Be different from the fabric after simple traditional amido silicon oil is put in order, can directly return something for repairs without handling through the fabric after the hydrophilic synergist arrangement of durability.
The hydrophilic synergist of amido silicon oil provided by the present invention (emulsion) durability 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, the hydrophilic synergist of amido silicon oil of the present invention can use before or after traditional amido silicon oil soft finish separately, perhaps used with bathing with traditional amino silicon oil emulsion; Should fully dissolve and mix before using.
Specifically comprise the steps: to adopt the hydrophilic synergist of amido silicon oil provided by the invention (emulsion) durability fabric to be put in order through the method for rolling of soaking.
The condition that said one method of rolling of soaking is put in order fabric is: fabric one soaks one and rolls working solution, and pressure is 2-5Kg/cm
2, pick-up rate 70-75%; 90-110 ℃ down bakes 60-120s under oven dry 60-120s, 140-160 ℃;
Said working solution is: the 1) aqueous solution of the hydrophilic synergist of said amido silicon oil, or 2) mixed aqueous solution of amido silicon oil and the hydrophilic synergist of said amido silicon oil; The mass concentration of the hydrophilic synergist of amido silicon oil is 0.05-10% in the said working solution.
When said working solution was the aqueous solution of the hydrophilic synergist of said amido silicon oil, said method also comprised following 1) or 2): 1) said fabric is carried out the step of pre-treatment with amido silicon oil; The step of 2) fabric after the said method processing being carried out post processing 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, course of reaction is simple.
2, good stability, consumption is few, and cost is low, and is applied widely, and technique for applying is simple to operation, both can also can use with bathing with amino silicon oil emulsion separately in the forward and backward use of amido silicon oil soft finish.
3, can give fabric fabulous hydrophily, and not influence 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 handling directly to return something for repairs.
4, after its arrangement, to do the time spent with fabric and combine more firmly with the form of chemical bond, the hydrophily of fabric has durability.
Description of drawings
Fig. 1 is the infrared spectrum of the hydrophilic synergist of amido silicon oil (emulsion) durability of embodiment 1 preparation.
Fig. 2 is the infrared spectrum of the hydrophilic synergist of amido silicon oil (emulsion) durability of embodiment 2 preparations.
Fig. 3 is the infrared spectrum of the hydrophilic synergist of amido silicon oil (emulsion) durability of embodiment 3 preparations.
Fig. 4 is the infrared spectrum of the hydrophilic synergist of amido silicon oil (emulsion) durability of embodiment 4 preparations.
Fig. 5 is the infrared spectrum of the hydrophilic synergist of amido silicon oil (emulsion) durability of embodiment 5 preparations.
The specific embodiment
The present invention will be described through specific embodiment below, but the present invention is not limited thereto.
Experimental technique described in the following embodiment like no specified otherwise, is conventional method; Said reagent and material like no specified otherwise, all can obtain from commercial sources.
Among the following embodiment the hydrophily method of testing of using and feel method of testing and standard following:
Hydrophily test: AATCC-79 method: cloth specimen (in air moisture regain one night) entirely is fixed on the cloth circle that stretches tight, uses the buret of titration nozzle diameter, be the 1cm place water that drips from the cloth cover height, and picking up counting as 1mm.When globule when reflectance is reduced to a complete opaque watermark gradually, stop timing, to test 3-5 point and average, it is short more that water droplet permeates diffusion time fully, explains that hydrophilicity is good more.
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, is 1 grade with unfinished blank cloth, and the grade regulation of the best is 5 grades, and other fabric is graded with respect to this standard.
1. the hydrophilic synergist of amido silicon oil (emulsion) durability is synthetic
The mixture of the allyl polyether of the end allyl polyoxy alkyl epoxy base ether of 79.0g Methyl Hydrogen Polysiloxane Fluid, 17.1g allyl glycidyl 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 chloroplatinic acid, catalyst consumption (in chloroplatinic acid) is according to the 30ppm of reactant gross mass (promptly 3 * 10
-5) add, insulation reaction 5 hours, low-volatile material is sloughed in decompression distillation then, and the transparency liquid that obtains is the hydrophilic synergist of amido silicon oil (emulsion) durability, 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 allyl glycidyl ether structural formula is CH
2=CHCH
2OCH
2(CHCH
2) O
End allyl 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.Can know 3050cm by Fig. 1
-1For the stretching vibration peak of C-H in the epoxy radicals, at 2970～2887cm
-1The place is in the polymer-CH
3With-CH
2The absworption peak of-group, 1640～1660cm
-1Be the characteristic absorption peak of C=C key in the excessive allyl compound, 1255cm
-1Be Si-CH
3In-CH
3The symmetrical deformation vibration absworption peak, 1130～1000cm
-1The place is the overlap peak of C-O-C stretching vibration and Si-O-Si stretching vibration absworption peak, 803cm
-1Near be Si-CH
3The stretching vibration absworption peak of middle Si-C, 1450cm
-1Be the flexural vibrations absworption peak of saturated c h bond, at 2280～2080cm
-1Do not have the characteristic absorption peak of Si-H to occur, this shows that Si-H disappears basically, and infrared spectrum can be verified and synthesize target product.
2. textile finishing and performance test
In deionized water, add 0.2% the hydrophilic synergist of above-mentioned durability; Be mixed with working solution (padding liquid) after fully mixing; Soak a technology of rolling to putting in order through the black plain weave pure cotton woven fabric after traditional amino silicon oil emulsion soft treatment through one; Find that the COTTON FABRIC infiltration osmotic effect after working solution is to traditional amino silicon oil emulsion soft finish is good, pressure is 3Kg/cm
2, pick-up rate 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 hydrophily adopts the water droplet osmosis to measure according to the AATCC-79 method.Test result is following:
Table 1 feel and hydrophily test result
The textile woven cloth 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 cloth of black plain weave) | Outward appearance | Standard deviation value | The K/S value |
| Tradition amido silicon oil arrangement back (before returning something for repairs) | Evenly, colourless flower | 0.21 | 8.2 |
| Tradition amido silicon oil arrangement back (back of returning something for repairs) | Tangible look flower is arranged | 0.95 | 9.4 |
| Through |
Evenly, colourless flower | 0.23 | 12.6 |
(dyestuff of redying use 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 measurement and color match appearance, the K/S value is big more, explains that the cloth specimen color is dark more; The K/S value is more little, and color is shallow more; Standard deviation value is big more, explains that the cloth specimen color is inhomogeneous more, and standard deviation value is more little, and account for color is even more)
Embodiment 2
1. the hydrophilic synergist of amido silicon oil (emulsion) durability is synthetic
The mixture of the allyl polyether of the allyl glycidyl 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, catalyst consumption (in platinum chloride) is according to the 50ppm of reactant gross mass (promptly 5 * 10
-5) add, insulation reaction 7 hours, low-volatile material is sloughed in decompression distillation then, and the transparency liquid that obtains is the hydrophilic synergist of amido silicon oil (emulsion) durability, 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 allyl glycidyl 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.Can know that by Fig. 2 synthetic product is a target product.
2. textile finishing and performance test
Earlier traditional amino silicon oil emulsion of 20% is made into the working solution of 40g/L; In this working solution, add 0.1% the hydrophilic synergist of above-mentioned durability then; After fully mixing, soak a technology of rolling through one the textile woven cloth of blueness is carried out soft finish, pressure is 2.7Kg/cm
2, pick-up rate 75% is dried 100 ℃ * 120s then, bakes 140 ℃ * 120s.5 professionals adopt the feel of hand digital palpation for examination of trauma evaluation fabric, and hydrophily adopts the water droplet osmosis to measure according to the AATCC-79 method.The result is following:
Table 3 feel and hydrophily test result
| Sample | Feel | Hydrophily/s | Wash the hydrophily/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 cloth; 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. the hydrophilic synergist of amido silicon oil (emulsion) durability is synthetic
The mixture of the allyl polyether of the end allyl polyoxy alkyl epoxy base ether of the Methyl Hydrogen Polysiloxane Fluid of 80.4g, 448.8g and 335g is dropped in the reactor, and logical nitrogen is also opened and is stirred, and is 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, catalyst consumption is (with 1; 3-divinyl-1; 1,3,3-tetramethyl disiloxane platinum complex meter) according to the 15ppm of reactant gross mass (promptly 1.5 * 10
-5) add, insulation reaction 6 hours, low-volatile material is sloughed in decompression distillation then, and the transparency liquid that obtains is the hydrophilic synergist of amido silicon oil (emulsion) durability, 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 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.Can know that by Fig. 3 synthetic product is a target product.
2. textile finishing and performance test
Earlier traditional amino silicon oil emulsion of 25% is made into the working solution of 40g/L; In this working solution, add 0.3% the hydrophilic synergist of above-mentioned durability then; After fully mixing, soak a technology of rolling through one red pure cotton knitting cloth is carried out soft finish, pressure is 3.5Kg/cm
2, pick-up rate 75% is dried 110 ℃ * 90s then, bakes 140 ℃ * 90s, and 5 professionals adopt the feel of hand digital palpation for examination of trauma evaluation fabric, and hydrophily adopts the water droplet osmosis to measure according to the AATCC-79 method.The result is following:
Table 4 feel and hydrophily test result
| Sample | Feel | Hydrophily/s | Wash the hydrophily/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 (back of returning something for repairs) | Evenly, colourless flower | 0.14 | 14.8 |
| Tradition amido silicon oil arrangement back (back of returning something for repairs) | Tangible look flower is arranged | 0.75 | 10.2 |
| Through embodiment 3 arrangements (back of returning something for repairs) | Evenly, colourless flower | 0.17 | 14.9 |
(dyestuff of redying use 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 measurement and color match appearance, the K/S value is big more, explains that the cloth specimen color is dark more; The K/S value is more little, and color is shallow more; Standard deviation value is big more, explains that the cloth specimen color is inhomogeneous more, and standard deviation value is more little, and account for color is even more)
Embodiment 4
1. the hydrophilic synergist of amido silicon oil (emulsion) durability is synthetic
The mixture of the end allyl polyoxy alkyl epoxy base ether of the allyl glycidyl 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 chloroplatinic acid, catalyst consumption (in chloroplatinic acid) is according to the 25ppm of reactant gross mass (promptly 2.5 * 10
-5) add, insulation reaction 5 hours, low-volatile material is sloughed in decompression distillation then, and the transparency liquid that obtains is the hydrophilic synergist of amido silicon oil (emulsion) durability, 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 allyl glycidyl ether structural formula is CH
2=CHCH
2OCH
2(CHCH
2) O
End allyl 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.Can know that by Fig. 4 synthetic product is a target product.
2. textile finishing and performance test
In deionized water, add 0.25% the hydrophilic synergist of above-mentioned durability; Be mixed with working solution after fully mixing; Soak a technology of rolling through one the woven cloth thing of white polyester-cotton blend is put in order, after baking through oven dry, again traditional amino silicon oil emulsion of 20% is made into the working solution of 30g/L; Soak the polyester-cotton fabric of a technology of rolling after to above-mentioned arrangement with this working solution through one then and carry out soft finish, pressure is 3Kg/cm
2, pick-up rate 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 hydrophily adopts the water droplet osmosis to measure according to the AATCC-79 method.The result is following:
Table 6 feel and hydrophily test result
| Sample | Feel | Hydrophily/s | Wash the hydrophily/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 |
The woven cloth of white twill polyester-cotton blend; 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. the hydrophilic synergist of amido silicon oil (emulsion) durability is synthetic
The mixture of the end allyl polyoxy alkyl epoxy base ether of the Methyl Hydrogen Polysiloxane Fluid of 44.4g and 150.6g is dropped in the reactor, and logical nitrogen is also opened and is stirred, and is warming up to 90 ℃, adds 1 in the dimethyl siloxane; 3-divinyl-1,1,3,3-tetramethyl disiloxane platinum complex (mass concentration 12%) 0.016g; Catalyst consumption (with 1,3-divinyl-1,1; 3,3-tetramethyl disiloxane platinum complex meter) 10ppm according to the reactant gross mass adds insulation reaction 8 hours; Low-volatile material is sloughed in decompression distillation then, and the transparency liquid that obtains is the hydrophilic synergist of amido silicon oil (emulsion) durability, 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 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.Can know that by Fig. 5 synthetic product is a target product.
2. textile finishing and performance test
Earlier traditional amino silicon oil emulsion of 20% is made into the working solution of 30g/L; In this working solution, add 0.4% the hydrophilic synergist of above-mentioned durability then; After fully mixing, soak a technology of rolling through one the woven cloth of green terylene is carried out soft finish, pressure is 3.3Kg/cm
2, pick-up rate 73% is dried 105 ℃ * 60s then, bakes 160 ℃ * 90s.5 professionals adopt the feel of hand digital palpation for examination of trauma evaluation fabric, and hydrophily adopts the water droplet osmosis to measure according to the AATCC-79 method.The result is following:
Table 7 feel and hydrophily test result
| Sample | Feel | Hydrophily/s | Wash the hydrophily/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 |
The woven cloth of green terylene; 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 (10)
1. the hydrophilic synergist of the amido silicon oil shown in the formula 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 a+b+c+d=1-20, a >=0, and b and d can not be 0 simultaneously, c and d can not be 0 simultaneously;
N＞m >=0, the integer between the m+n=5-25;
Integer between the p+q=0-25, and divide following situation to 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. a method for preparing the hydrophilic synergist of amido silicon oil shown in the formula I comprises the steps: under the oxygen free condition, and Methyl Hydrogen Polysiloxane Fluid and allyl compound are reacted under the platinum catalyst effect, obtains the hydrophilic synergist of said amido silicon oil;
Wherein, the structural formula of said 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;
Said allyl compound by following a)-d) in any one group of material form:
A) allyl glycidyl ether, end allyl end ring oxo-compound A and allyl polyether;
Wherein, the structural formula of said allyl glycidyl ether is CH
2=CHCH
2OCH
2(CHCH
2) O;
The structural formula of said end allyl end ring oxo-compound A 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 said 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) said end allyl end ring oxo-compound A and said allyl polyether;
C) said allyl glycidyl ether and end allyl end ring oxo-compound B;
The structural formula of said end allyl end ring oxo-compound B 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) said end allyl end ring oxo-compound B.
3. method according to claim 2 is characterized in that: the reaction temperature of said reaction is 70-120 ℃, and the time is 1-12 hour;
In the said reaction, the amount of substance ratio of the C=C in the Si-H in the said Methyl Hydrogen Polysiloxane Fluid and the allyl compound is 1.0: (1.0-5.0), and preferred 1.0: (1.1-1.6).
4. according to claim 2 or 3 described methods; It is characterized in that: said platinum catalyst is absolute ethyl alcohol or the aqueous isopropanol of platinum chloride, aqueous isopropanol and dimethyl siloxane and 1 of chloroplatinic acid; 3-divinyl-1; 1,3, any one in the mixture of 3-tetramethyl disiloxane platinum complex; The consumption of said platinum catalyst is counted the 10-100ppm of reactant gross mass with platinum chloride, chloroplatinic acid or platinum complex, preferred 10-50ppm.
5. according to each said fixed method among the claim 2-4, it is characterized in that: among the said preparation method, hydrophilic oxirane segment C
2H
4The ratio that O accounts for preparation product gross mass is 20%-75%, and oxirane segment C
2H
4O accounts for the mass fraction of preparation product greater than expoxy propane segment C
3H
6O; Has reactive epoxide group-(CHCH
2) the O ratio that accounts for preparation product gross mass is 1%-10%.
6. according to each described method among the claim 2-5, it is characterized in that: said method also is included in the step that vacuumizes decompression distillation after reaction finishes.
7. the application of the hydrophilic synergist of the said amido silicon oil of claim 1 in textile finishing.
8. the method that fabric is put in order comprises the steps: to adopt the hydrophilic synergist of the said amido silicon oil of claim 1 through the method for rolling of soaking fabric to be put in order.
9. method according to claim 8 is characterized in that: the condition that said one method of rolling of soaking is put in order fabric is: fabric one soaks one and rolls working solution, and pressure is 2-5Kg/cm
2, pick-up rate 70-75%; 90-110 ℃ down bakes 60-120s under oven dry 60-120s, 140-160 ℃;
Wherein, said working solution is: the 1) aqueous solution of the hydrophilic synergist of said amido silicon oil, or 2) mixed aqueous solution of amido silicon oil and the hydrophilic synergist of said amido silicon oil; The mass concentration of the hydrophilic synergist of amido silicon oil is 0.05-10% in the said working solution.
10. method according to claim 9 is characterized in that: said working solution is the aqueous solution of the hydrophilic synergist of said amido silicon oil, and said method also comprises following 1) and/or 2):
1) said fabric is carried out the step of pre-treatment with amido silicon oil;
The step of 2) fabric after the said method processing being carried out post processing with amido silicon oil.
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| CN103556508A (en) * | 2013-11-05 | 2014-02-05 | 常熟市宝沣特种纤维有限公司 | Printing method of aramid-viscose blended camouflage printed fabric |
| CN107226909A (en) * | 2017-07-31 | 2017-10-03 | 王金桢 | A kind of fabric softener epoxy modified polysiloxane preparation method processed |
| 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 |
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| CN103556508A (en) * | 2013-11-05 | 2014-02-05 | 常熟市宝沣特种纤维有限公司 | Printing method of aramid-viscose blended camouflage printed fabric |
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| 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 |
| CN117306263A (en) * | 2023-10-18 | 2023-12-29 | 广州蓝博纺织品有限公司 | Far infrared anion antibacterial multifunctional health quilt and preparation method thereof |
| 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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