CN111676701A - Amino modified polysiloxane softening agent and preparation method thereof - Google Patents
Amino modified polysiloxane softening agent and preparation method thereof Download PDFInfo
- Publication number
- CN111676701A CN111676701A CN202010729096.0A CN202010729096A CN111676701A CN 111676701 A CN111676701 A CN 111676701A CN 202010729096 A CN202010729096 A CN 202010729096A CN 111676701 A CN111676701 A CN 111676701A
- Authority
- CN
- China
- Prior art keywords
- amino
- modified polysiloxane
- polysiloxane
- heating
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/2243—Mono-, di-, or triglycerides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Polymers (AREA)
Abstract
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.
Description
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.
Examples
Example 1
The amino modified polysiloxane softening agent comprises, by weight, 30 parts of polysiloxane, 10 parts of nonionic surfactant, 5 parts of stabilizer, 5 parts of emulsifier and 50 parts of water, wherein the emulsifier is polyether emulsifier, the polyether emulsifier is polyoxyethylene lauryl ether, and CAS (CAS) number is as follows: 9002-92-0, purchased from Haian petrochemical plant of Jiangsu province. The polysiloxane is amino modified polysiloxane, and 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 ℃, stirring while heating, adding diethanol amine into the four-neck flask, and reacting for 3 hours at the temperature of 70 ℃, wherein the CAS number of the gamma-chloropropylmethyldimethoxysilane is as follows: 18171-19-2, available from Shanghai Yi potential chemical Co., Ltd, and the CAS number of diethanolamine is: 111-42-2, available from Zibo Mulberry phenanthrene Jingmao, Inc.;
(2) after the step (1) is finished, reducing the temperature of the compound obtained in the step (1) to 40 ℃, then adding distilled water, and hydrolyzing for 6h, wherein the mass ratio of the gamma-chloropropylmethyldimethoxysilane to the diethanolamine to the distilled water is 1: 2: 1;
(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 ℃, adding hexamethylcyclotrisiloxane and tetramethylammonium hydroxide, heating to 100 ℃ for reaction for 5 hours, heating to 120 ℃ after the reaction is finished, keeping for 2 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.
the CAS number of hexamethylcyclotrisiloxane is: 541-05-9, available from Gnaphaline Biotechnology, Inc., of Wuhan Hua. CAS number for tetramethylammonium hydroxide is: 10424-65-4, available from Tianhua Biotech, Inc., Longyan.
The nonionic surfactant is glyceryl monostearate, and the CAS number of the glyceryl monostearate is as follows: 123-94-4, purchased from Leyan chemical mall. The stabilizer comprises dibutyltin maleate, phosphite ester, epoxidized soybean oil and hindered phenol antioxidant. The CAS number of the dibutyltin maleate is as follows: 78-04-6, available from Kaiban chemical commerce. The weight ratio of the dibutyltin maleate, the phosphite ester, the epoxidized soybean oil to the hindered phenol antioxidant is 5: 2: 3: 1. the phosphite ester is purchased from Tianjin Jinheng blue sea technology limited, the epoxidized soybean oil is purchased from Jiangsu Chuangteng New Material technology limited, the hindered phenol antioxidant is 2-tert-butyl-4-methylphenol, is purchased from Nanjing Ningkang chemical industry limited, and has the CAS number: 2409-55-4.
The preparation method of the amino-modified polysiloxane softener in the embodiment comprises the following steps:
(1) adding the amino modified polysiloxane into a reaction kettle, stirring, and then sequentially adding lauryl alcohol polyoxyethylene ether, glyceryl monostearate, dibutyltin maleate, phosphite ester, epoxidized soybean oil and 2-tert-butyl-4-methylphenol;
(2) adding acetic acid into the mixture obtained in the step (1), and stirring, wherein the mass ratio of the acetic acid to the dibutyltin maleate 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. The CAS number of the ethylene glycol is 203-473-3, and the ethylene glycol is purchased from Simian metallocene chemical Co. The CAS number of the acetic acid is: 64-19-7.
Example 2
The difference from example 1 is that: the amino modified polysiloxane softening agent comprises, by weight, 40 parts of polysiloxane, 20 parts of nonionic surfactant, 6 parts of stabilizer, 7 parts of emulsifier and 60 parts of water, wherein the emulsifier is polyether emulsifier. The polysiloxane is amino modified polysiloxane, and 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 75 ℃, stirring while heating, adding diethanolamine into the four-neck flask, and reacting for 4 hours at 75 ℃;
(2) after the step (1) is finished, reducing the temperature of the compound obtained in the step (1) to 45 ℃, then adding distilled water, and hydrolyzing for 7h, wherein the mass ratio of the gamma-chloropropylmethyldimethoxysilane to the diethanolamine to the distilled water is 1: 3: 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 65 ℃, adding hexamethylcyclotrisiloxane and tetramethylammonium hydroxide, heating to 100 ℃ for reaction for 5 hours, heating to 130 ℃ after the reaction is finished, keeping for 3 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.
example 3
The difference from example 1 is that: the amino modified polysiloxane softener comprises the raw materials of, by weight, 50 parts of polysiloxane, 25 parts of nonionic surfactant, 8 parts of stabilizer, 10 parts of emulsifier and 70 parts of water, wherein the emulsifier is polyether emulsifier. The polysiloxane alkyl is amino modified polysiloxane, and 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 80 ℃, stirring while heating, adding diethanolamine into the four-neck flask, and reacting for 5 hours at 80 ℃;
(2) after the step (1) is finished, reducing the temperature of the compound obtained in the step (1) to 50 ℃, then adding distilled water, and hydrolyzing for 8 h;
(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 70 ℃, adding hexamethylcyclotrisiloxane and tetramethylammonium hydroxide, heating to 100 ℃ for reaction for 5 hours, heating to 140 ℃ after the reaction is finished, keeping for 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.
comparative example 1
The difference from example 1 is that: the polysiloxane is amino modified polysiloxane, and 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 75 ℃, stirring while heating, adding methanolamine into the four-neck flask, and reacting for 4 hours at 75 ℃;
(2) after the step (1) is finished, reducing the temperature of the compound obtained in the step (1) to 45 ℃, then adding distilled water, and hydrolyzing for 7h, wherein the mass ratio of the gamma-chloropropylmethyldimethoxysilane to the methanolamine to the distilled water is 1: 2: 1;
(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 65 ℃, adding hexamethylcyclotrisiloxane and tetramethylammonium hydroxide, heating to 100 ℃ for reaction for 5 hours, heating to 130 ℃ after the reaction is finished, keeping for 3 hours to decompose the tetramethylammonium hydroxide, and then carrying out reduced pressure distillation to remove low-boiling-point substances from the mixture at the temperature of 100 ℃ to obtain amino-modified polysiloxane, wherein the mass ratio of the liquid mixture to the hexamethylcyclotrisiloxane to the tetramethylammonium hydroxide is as follows: 10: 8: 1. the methanolamine is purchased from Shandong-West Asia chemical technology Co. :
comparative example 2
The difference from example 1 is that: the polysiloxane is amino modified polysiloxane, and 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 75 ℃, stirring while heating, adding diethylamine into the four-neck flask, and reacting for 4 hours at 75 ℃;
(2) after the step (1) is finished, reducing the temperature of the compound obtained in the step (1) to 45 ℃, then adding distilled water, and hydrolyzing for 7h, wherein the mass ratio of the gamma-chloropropylmethyldimethoxysilane to the diethylamine to the distilled water is 1: 2: 1;
(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 65 ℃, adding hexamethylcyclotrisiloxane and tetramethylammonium hydroxide, heating to 100 ℃ for reaction for 5 hours, heating to 130 ℃ after the reaction is finished, keeping for 3 hours to decompose the tetramethylammonium hydroxide, and then carrying out reduced pressure distillation to remove low-boiling-point substances from the mixture at the temperature of 100 ℃ to obtain amino-modified polysiloxane, wherein the mass ratio of the liquid mixture to the hexamethylcyclotrisiloxane to the tetramethylammonium hydroxide is as follows: 10: 8: 1. the CAS number of the diethylamine is: 109-89-7, available from aladdin.
Comparative example 3
The difference from example 1 is that: in this example, the surfactant composition does not contain a nonionic surfactant, and contains an ionic cationic surfactant, and the mass ratio of the cationic surfactant to the polysiloxane is 1: 2, the cationic surfactant is hexadecyl trimethyl ammonium bromide, which is purchased from Zhengzhou Yiguan chemical products Co., Ltd, and the product number is as follows: 469-2356.
Comparative example 4
The difference from example 1 is that: the nonionic surfactant is not included in this example.
Comparative example 5
The difference from example 1 is that: in this example, the surfactant composition does not contain a nonionic surfactant, and contains an anionic surfactant, and the mass ratio of the anionic surfactant to the polysiloxane is 1: 2, the anionic surfactant is sodium dodecyl sulfate, and the CAS number is as follows: 151-21-3, available from Utility chemical Co., Ltd, Suzhou.
Performance testing
The specific test method comprises the following steps: the amino modified polysiloxane softening agents obtained in examples 1-3 to comparative examples 1-5 are respectively used for padding finishing of 150 pieces of pure cotton white fabrics, and the specific method is as follows: adding an amino modified polysiloxane softening agent into water to prepare finishing bath lotion, wherein the mass ratio of the amino modified polysiloxane softening agent to the water is 1: and 5, soaking the pure cotton white fabric into the finishing bath solution for 5 hours, fishing out, rolling by using a padder to remove redundant finishing solution, and finally drying the pure cotton white fabric by using a dryer to obtain a test sample.
Testing one: taking 50 test samples from each test sample obtained in each example and each test sample obtained in each comparative example, selecting 10 volunteers to respectively test the hand feeling of the test samples, wherein 0-5 smooth and soft hand feeling is poor, 5-30 smooth and soft hand feeling is good, and 30-50 smooth and soft hand feeling is good.
And (2) testing: taking 50 test samples from each of the test samples obtained in each of the examples and comparative examples, sucking more than 5ml of water with a 10ml dropper, dropping 1ml of water at a height of 3cm from the test sample, recording the time taken for the test sample to completely suck water, and finally calculating the average time taken for each of the examples and comparative examples.
And (3) testing: taking 50 test samples from each test sample obtained in each example and each test sample obtained in each comparative example, washing the test samples for 30min by using a washing machine under the same condition, then airing the test samples, repeating the steps of washing and airing for 5 times, and finally observing whether the test samples in each example and each comparative example have yellowing phenomenon and hand feeling softness, wherein the evaluation method of the hand feeling softness is as described in the test I.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010729096.0A CN111676701A (en) | 2020-07-27 | 2020-07-27 | Amino modified polysiloxane softening agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010729096.0A CN111676701A (en) | 2020-07-27 | 2020-07-27 | Amino modified polysiloxane softening agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111676701A true CN111676701A (en) | 2020-09-18 |
Family
ID=72438302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010729096.0A Withdrawn CN111676701A (en) | 2020-07-27 | 2020-07-27 | Amino modified polysiloxane softening agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111676701A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114808460A (en) * | 2021-06-28 | 2022-07-29 | 染格材料科技(上海)有限公司 | Softening agent and preparation method and application thereof |
-
2020
- 2020-07-27 CN CN202010729096.0A patent/CN111676701A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114808460A (en) * | 2021-06-28 | 2022-07-29 | 染格材料科技(上海)有限公司 | Softening agent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102643435B (en) | Supersoft hydrophilic block silicone oil compound and preparation method thereof | |
| US7329707B2 (en) | Partially quaternised, amino-functional organopolysiloxanes and their use in aqueous systems | |
| EP2518101B1 (en) | Organo-functional silicone in emulsion systems and process for preparing same | |
| JP4663962B2 (en) | Modified polyorganosiloxane, its aqueous emulsion, its production and its use | |
| EP1753906B9 (en) | Textile treatments using fluoropolymer-branched silicone polyethers | |
| CN102549046A (en) | Novel polysiloxanes having quaternary ammonium groups and use thereof | |
| CN111877020B (en) | Modified silicone oil softening agent and preparation method thereof | |
| CN102644200B (en) | Super-soft finishing agent of silicone oil | |
| CN1930341A (en) | Treating textiles with emulsions containing silicone resins | |
| EP0200325B1 (en) | Method of improving the draining of water from textiles during a laundering operation | |
| JPH04289276A (en) | Method for softening fiber substance and impart- ing hydrophilic nature thereto using polyorgano- silane containing composition | |
| EP0399706A2 (en) | Method of treating fibrous materials | |
| JP2007532795A5 (en) | ||
| KR100798186B1 (en) | Water repellent textile finishes and method of making | |
| US6472468B1 (en) | Fluorinated polysiloxane, making method, and fiber or fabric treating agent composition | |
| CN110627828A (en) | Organosilicon quaternary ammonium salt for improving antibacterial performance and preparation method and application thereof | |
| CN111676701A (en) | Amino modified polysiloxane softening agent and preparation method thereof | |
| CN102660029B (en) | Cation modified supersoft hydrophilic block silicone oil compound and preparation method and application | |
| US7629415B2 (en) | Highly concentrated self-emulsifying preparations containing organopolysiloxanes and alkylammonium compounds and use thereof in aqueous systems | |
| CN113861425B (en) | Co-modified organic silicon composition and preparation method thereof | |
| CA2449955A1 (en) | Polysiloxane and textile adjunct comprising a polysiloxane | |
| CN102505495B (en) | High-elastic smooth silicon softener and preparation method and application thereof | |
| US6579325B1 (en) | Silicone compositions for treating wool materials | |
| CN101089280A (en) | Preparation for finishing textile fibre and product and improved feel of textile | |
| CN113248713B (en) | Low-yellowing amino silicone oil and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200918 |
|
| WW01 | Invention patent application withdrawn after publication |