阅读说明：本技术 一种氨基改性的聚硅氧烷柔软剂及其制备方法 (Amino modified polysiloxane softening agent and preparation method thereof ) 是由 吴卫勇 于 2020-07-27 设计创作，主要内容包括：本发明公开了一种氨基改性的聚硅氧烷柔软剂及其制备方法,按重量份计,其原料包括聚硅氧烷30-50份、非离子型表面活性剂10-25份、稳定剂5-8份、乳化剂5-10份、水50-70份,所述乳化剂为聚醚型乳化剂。所述聚硅氧烷烷为氨基改性的聚硅氧烷。氨基改性的聚硅氧烷能够提高柔软剂的抗黄变性能。用二乙醇胺对γ-氯丙基甲基二甲氧基硅烷进行改性,使硅烷中引入仲氨基和羟基,增加硅烷的亲水性和抗黄变性能,使整理过的织物吸汗透气,提高了织物的舒适性能。使用聚醚型乳化剂对氨基改性的聚硅氧烷进行乳化,能够提高柔软剂的亲水性能和去污性能。(The invention discloses an amino modified polysiloxane softening agent and a preparation method thereof, wherein the raw materials comprise, by weight, 30-50 parts of polysiloxane, 10-25 parts of nonionic surfactant, 5-8 parts of stabilizer, 5-10 parts of emulsifier and 50-70 parts of water, and the emulsifier is polyether emulsifier. The polysiloxane alkane is amino modified polysiloxane. The amino modified polysiloxane can improve the anti-yellowing performance of the softening agent. The gamma-chloropropyl methyl dimethoxy silane is modified by diethanol amine, so that secondary amino and hydroxyl are introduced into the silane, the hydrophilicity and anti-yellowing performance of the silane are improved, the finished fabric absorbs sweat and is breathable, and the comfort performance of the fabric is improved. The polyether emulsifier is used for emulsifying the amino modified polysiloxane, so that the hydrophilic performance and the decontamination performance of the softening agent can be improved.)

1. The amino modified polysiloxane softener is characterized by comprising, by weight, 30-50 parts of polysiloxane, 10-25 parts of nonionic surfactant, 5-8 parts of stabilizer, 5-10 parts of emulsifier and 50-70 parts of water, wherein the emulsifier is polyether emulsifier.

2. The amino-modified polysiloxane softener according to claim 1, wherein the polysiloxane is an amino-modified polysiloxane.

3. The amino-modified polysiloxane softener according to claim 2, wherein the preparation method of the amino-modified polysiloxane comprises the following steps:

(1) introducing nitrogen into a four-neck flask, adding gamma-chloropropylmethyldimethoxysilane, heating the gamma-chloropropylmethyldimethoxysilane to 70-80 ℃, stirring while heating, adding diethanolamine into the four-neck flask, and reacting for 3-5 hours at 70-80 ℃;

(2) after the step (1) is finished, reducing the temperature of the compound obtained in the step (1) to 40-50 ℃, then adding distilled water, and hydrolyzing for 6-8h, wherein the mass ratio of the gamma-chloropropylmethyldimethoxysilane to the diethanolamine to the distilled water is 1: 2-3: 1-3;

(3) distilling the mixture obtained in the step (2) under reduced pressure to remove redundant water, thus obtaining a liquid mixture;

(4) introducing nitrogen into a three-neck flask, adding the liquid mixture in the step (3) into the three-neck flask, starting heating and stirring, heating to 60-70 ℃, adding hexamethylcyclotrisiloxane and tetramethylammonium hydroxide, heating to 100 ℃ for reaction for 5 hours, heating to 120-140 ℃ after the reaction is finished, keeping for 2-4 hours to decompose the tetramethylammonium hydroxide, cooling to 100 ℃, and carrying out reduced pressure distillation to remove low-boiling-point substances to obtain the amino-modified polysiloxane, wherein the mass ratio of the liquid mixture to the hexamethylcyclotrisiloxane to the tetramethylammonium hydroxide is as follows: 10: 8: 1.

4. the amino-modified polysiloxane softener according to claim 1, wherein the polyether emulsifier is polyoxyethylene lauryl ether.

5. The amino-modified silicone softener according to claim 1, wherein said nonionic surfactant is glyceryl monostearate.

6. The amino-modified polysiloxane softener of claim 1, wherein the stabilizer comprises organotin.

7. The amino-modified polysiloxane softener according to claim 6, wherein the organotin is dibutyltin maleate.

8. The amino-modified polysiloxane softener of claim 7 wherein said stabilizer further comprises a phosphite, epoxidized soybean oil and hindered phenolic antioxidant.

9. The amino-modified polysiloxane softener according to claim 8, wherein the weight ratio of dibutyltin maleate, phosphite ester, epoxidized soybean oil and hindered phenol antioxidant is 5: 2: 3: 1.

10. a method of preparing an amino-modified polysiloxane softener according to any one of claims 1 to 9, comprising the steps of:

(1) adding polysiloxane into a reaction kettle, stirring, and then sequentially adding an emulsifier, a nonionic surfactant and a stabilizer;

(2) adding acetic acid into the mixture obtained in the step (1), and stirring, wherein the mass ratio of the acetic acid to the stabilizer is 1: 5;

(3) adding water and ethylene glycol into the mixture obtained in the step (2), wherein the mass ratio of the water to the ethylene glycol is 100: 1, obtaining the amino modified polysiloxane softening agent.

Technical Field

The application belongs to the technical field of textile auxiliary agents, and particularly relates to a polysiloxane softening agent and a preparation method thereof

Background

The textile auxiliary is an important chemical substance which needs to be added in the textile fiber process, and the performance of the fabric is improved by adding the textile auxiliary. During the processing of the textile, the hand feeling of the textile becomes rough after being treated for many times, and the common synthetic fiber fabrics are worse, especially the superfine fiber fabrics. In order to make the fabric have soft, smooth and comfortable hand feeling, the fabric needs to be finished, and the finishing is widely performed by using a softening agent at present. In addition, a large amount of softening agents are used in the processes of spinning chemical fibers, spinning various fibers, weaving various fibers and the like, and the phenomena of scratch, strip defect and the like are easily caused because the mutual friction between fabrics and between the fabrics and equipment is increased along with the large amount of use of high-speed and small bath ratio modes in textile processing. The use of a softening agent allows the fibers themselves to have a soft smoothness compatible with the processing conditions to avoid damage. After the existing polysiloxane softener finishes fabrics, the fabrics have poor softness and poor yellowing resistance, and the softness of the fabrics is reduced to a certain extent after the fabrics are washed by water for several times.

Disclosure of Invention

In order to solve the technical problems, the invention provides an amino modified polysiloxane softening agent, which comprises, by weight, 30-50 parts of polysiloxane, 10-25 parts of nonionic surfactant, 5-8 parts of stabilizer, 5-10 parts of emulsifier and 50-70 parts of water, wherein the emulsifier is polyether emulsifier.

Preferably, the polysiloxane is an amino-modified polysiloxane.

Preferably, the preparation method of the amino-modified polysiloxane comprises the following steps:

(1) introducing nitrogen into a four-neck flask, adding gamma-chloropropylmethyldimethoxysilane, heating the gamma-chloropropylmethyldimethoxysilane to 70-80 ℃, stirring while heating, adding diethanolamine into the four-neck flask, and reacting for 3-5 hours at 70-80 ℃;

(2) after the step (1) is finished, reducing the temperature of the compound obtained in the step (1) to 40-50 ℃, then adding distilled water, and hydrolyzing for 6-8h, wherein the mass ratio of the gamma-chloropropylmethyldimethoxysilane to the diethanolamine to the distilled water is 1: 2-3: 1-3;

(3) distilling the mixture obtained in the step (2) under reduced pressure to remove redundant water, thus obtaining a liquid mixture;

(4) introducing nitrogen into a three-neck flask, adding the liquid mixture in the step (3) into the three-neck flask, starting heating and stirring, heating to 60-70 ℃, adding hexamethylcyclotrisiloxane and tetramethylammonium hydroxide, heating to 100 ℃ for reaction for 5 hours, heating to 120-140 ℃ after the reaction is finished, keeping for 2-4 hours to decompose the tetramethylammonium hydroxide, cooling to 100 ℃, and carrying out reduced pressure distillation to remove low-boiling-point substances to obtain the amino-modified polysiloxane, wherein the mass ratio of the liquid mixture to the hexamethylcyclotrisiloxane to the tetramethylammonium hydroxide is as follows: 10: 8: 1.

preferably, the polyether type emulsifier is polyoxyethylene lauryl ether.

Preferably, the nonionic surfactant is glyceryl monostearate.

Preferably, the stabilizer comprises organotin.

Preferably, the organotin is dibutyltin maleate.

Preferably, the stabilizer further comprises phosphite ester, epoxidized soybean oil and hindered phenol antioxidant.

Preferably, the weight ratio of the dibutyltin maleate to the phosphite to the epoxidized soybean oil to the hindered phenol antioxidant is 5: 2: 3: 1.

in a second aspect, the present invention provides a method for preparing an amino-modified polysiloxane softener, comprising the following steps:

(1) adding polysiloxane into a reaction kettle, stirring, and then sequentially adding an emulsifier, a nonionic surfactant and a stabilizer;

(2) adding acetic acid into the mixture obtained in the step (1), and stirring, wherein the mass ratio of the acetic acid to the stabilizer is 1: 5;

(3) adding water and ethylene glycol into the mixture obtained in the step (2), wherein the mass ratio of the water to the ethylene glycol is 100: 1, obtaining the amino modified polysiloxane softening agent.

Has the advantages that: the softening agent comprises amino modified polysiloxane, wherein the amino is a secondary amino, so that the yellowing resistance of the softening agent can be improved. The gamma-chloropropyl methyl dimethoxy silane is modified by diethanol amine, so that secondary amino and hydroxyl are introduced into the silane, the hydrophilicity, softness and yellowing resistance of the silane are improved, the finished fabric absorbs sweat and is breathable, and the comfort performance of the fabric is improved. The polyether emulsifier is used for emulsifying the amino modified polysiloxane, so that the hydrophilic performance and the decontamination performance of the softening agent can be improved. The nonionic surfactant is used for dispersing all the substances, the compatibility among all the components is improved, the stabilizer, the phosphite ester, the epoxidized soybean oil and the hindered phenol antioxidant are added into the softening agent, the stability of the performance of the softening agent is ensured, and the demulsification condition is prevented.

Detailed Description

For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.

In order to solve the problems, the invention provides an amino modified polysiloxane softening agent, which comprises the following raw materials, by weight, 30-50 parts of polysiloxane, 10-25 parts of nonionic surfactant, 5-8 parts of stabilizer, 5-10 parts of emulsifier and 50-70 parts of water, wherein the emulsifier is polyether emulsifier.

Polysiloxanes are polymers with repeating Si-O bonds as the backbone and organic groups directly attached to the silicon atom. It is customary to refer to silane monomers and polysiloxanes collectively as organosilicon compounds and to refer to polysiloxane liquids as silicone oils, which are generally classified into two types, methyl silicone oils and modified silicone oils. The most commonly used silicone oil, methyl silicone oil, is also called common silicone oil, organic groups of the silicone oil are all methyl, and the methyl silicone oil has good chemical stability, insulating property and hydrophobic property. It is prepared through hydrolysis of dimethyldichlorosilane in water to obtain initial condensed ring body, cracking and rectifying to obtain low ring body, mixing the ring body, sealing agent and catalyst together to obtain various mixture with different polymerization degree, and vacuum distillation to eliminate low-boiling point matter to obtain silicone oil.

Preferably, the polysiloxane is an amino-modified polysiloxane.

Preferably, the preparation method of the amino-modified polysiloxane comprises the following steps:

(1) introducing nitrogen into a four-neck flask, adding gamma-chloropropylmethyldimethoxysilane, heating the gamma-chloropropylmethyldimethoxysilane to 70-80 ℃, stirring while heating, adding diethanolamine into the four-neck flask, and reacting for 3-5 hours at 70-80 ℃;

(2) after the step (1) is finished, reducing the temperature of the compound obtained in the step (1) to 40-50 ℃, then adding distilled water, and hydrolyzing for 6-8h, wherein the mass ratio of the gamma-chloropropylmethyldimethoxysilane to the diethanolamine to the distilled water is 1: 2-3: 1-3;

(3) distilling the mixture obtained in the step (2) under reduced pressure to remove redundant water, thus obtaining a liquid mixture;

(4) introducing nitrogen into a three-neck flask, adding the liquid mixture in the step (3) into the three-neck flask, starting heating and stirring, heating to 60-70 ℃, adding hexamethylcyclotrisiloxane and tetramethylammonium hydroxide, heating to 100 ℃ for reaction for 5 hours, heating to 120-140 ℃ after the reaction is finished, keeping for 2-4 hours to decompose the tetramethylammonium hydroxide, cooling to 100 ℃, and carrying out reduced pressure distillation to remove low-boiling-point substances to obtain the amino-modified polysiloxane, wherein the mass ratio of the liquid mixture to the hexamethylcyclotrisiloxane to the tetramethylammonium hydroxide is as follows: 10: 8: 1.

preferably, the polyether type emulsifier is polyoxyethylene lauryl ether.

Preferably, the nonionic surfactant is glyceryl monostearate.

The nonionic surfactant is a surfactant that does not generate ions in an aqueous solution. Distinguished from anionic surfactants and cationic surfactants. Its solubility in water is due to its functional groups with a strong affinity for water. Compared with the anionic surfactant, the nonionic surfactant has higher emulsifying capacity and certain hard water resistance.

Preferably, the stabilizer comprises organotin.

Preferably, the organotin is dibutyltin maleate.

Chemicals that increase the stability of solutions, colloids, solids, and mixtures are called stabilizers. It can slow down reaction, maintain chemical equilibrium, reduce surface tension, and prevent photo, thermal or oxidative decomposition. The greatest advantages of organotin are excellent transparency, thermal stability, nontoxicity and good compatibility.

Preferably, the stabilizer further comprises phosphite ester, epoxidized soybean oil and hindered phenol antioxidant.

Preferably, the weight ratio of the dibutyltin maleate to the phosphite to the epoxidized soybean oil to the hindered phenol antioxidant is 5: 2: 3: 1.

the second aspect of the present invention provides a preparation method of the amino modified polysiloxane softener, comprising the following steps:

(1) adding polysiloxane into a reaction kettle, stirring, and then sequentially adding an emulsifier, a nonionic surfactant and a stabilizer;

(2) adding acetic acid into the mixture obtained in the step (1), and stirring, wherein the mass ratio of the acetic acid to the stabilizer is 1: 5;

(3) adding water and ethylene glycol into the mixture obtained in the step (2), wherein the mass ratio of the water to the ethylene glycol is 100: 1, obtaining the amino modified polysiloxane softening agent.

In addition, the starting materials used are all commercially available, unless otherwise specified.

The softening agent comprises amino modified polysiloxane, the main chain of the polysiloxane is very flexible, the energy required by rotation around a Si-O bond is almost zero, the rotation of the polysiloxane is free and can rotate for 360 degrees, and the flexibility of the polysiloxane is determined by the characteristic. However, the affinity between silicone and fabric is not strong and it is not resistant to washing, and the softness of the finished fabric after washing is deteriorated. The polysiloxane modified by amino can solve the problem of weak affinity of polysiloxane finished fabrics, and because the polarity of amino is strong, the amino interacts with hydroxyl, carboxyl and the like on the surface of fibers to form very firm orientation and adsorption with the fibers, so that the finished fabrics can maintain the soft performance for a long time. The flexibility of the Si-O bond main chain lowers the static friction coefficient between the fibers, and the fibers start to slide with a small force, so that the fibers feel soft. The gamma-chloropropyl methyl dimethoxy silane is modified by diethanol amine, so that secondary amino and hydroxyl are introduced into the silane, the hydrophilicity and anti-yellowing performance of the silane are improved, the finished fabric absorbs sweat and is breathable, and the comfort performance of the fabric is improved. Due to the higher steric hindrance of the secondary amino group, the phenomenon that the amino group is oxidized to cause yellowing can be prevented.