CN115368575B - Water-repellent and oil-repellent fabric finishing agent, finishing agent stock solution and preparation method thereof - Google Patents
Water-repellent and oil-repellent fabric finishing agent, finishing agent stock solution and preparation method thereof Download PDFInfo
- Publication number
- CN115368575B CN115368575B CN202211306442.XA CN202211306442A CN115368575B CN 115368575 B CN115368575 B CN 115368575B CN 202211306442 A CN202211306442 A CN 202211306442A CN 115368575 B CN115368575 B CN 115368575B
- Authority
- CN
- China
- Prior art keywords
- repellent
- finishing agent
- oil
- water
- hydroxyl
- 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.)
- Active
Links
Images
Classifications
-
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- 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
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
-
- 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
- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
-
- 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
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the field of textile finishing agents, in particular to a water-repellent and oil-repellent fabric finishing agent, a finishing agent stock solution and a preparation method thereof. Firstly, mixing double-end hydroxyl silicone oil and double-end hydroxyl perfluoropolyether alcohol, adding a solvent, heating to carry out dehydration condensation reaction to obtain a perfluoropolyether-silicone oil chain segment with active hydroxyl at two ends; and then adding polyether amine, and carrying out condensation reaction on active hydroxyl and amino under a heating condition to obtain the amino-terminated block fluorosilicone finishing agent. According to the invention, the silicone oil chain segment, the perfluoropolyether chain segment and the polyether amine chain segment are combined into a block structure, so that the finishing agent with good water and oil repellency is obtained, and the silicone oil chain segment of the finishing agent has high stability and can improve the softness of fabrics; the perfluoropolyether chain segment can improve the water and oil repellency and the smoothness of the fabric; the polyether amine segments provide a fluffy and smooth feel to the fabric.
Description
Technical Field
The invention relates to the field of textile finishing agents, in particular to a water-repellent and oil-repellent fabric finishing agent, a finishing agent stock solution and a preparation method thereof.
Background
People often contact with water in daily life, so that the requirement of people on waterproofing of the worn clothes is met, and the production of waterproof fabrics is promoted objectively. The water-repellent and oil-repellent finishing is a method for changing the surface performance of the fabric by adding a finishing agent on the fabric so that the fabric is not easily wetted or stained by water and common oil stains, and the used finishing agent is the water-repellent and oil-repellent finishing agent.
The traditional water-repellent and oil-repellent finishing method mainly comprises the following steps: 1) The compact waterproof moisture permeable fabric is tightly woven by adopting superfine fibers, has a certain waterproof effect, can only prevent water for a short time, cannot prevent water from permeating, has no oil repellency, has poor tearing performance and hard hand feeling. 2) The film lamination generally refers to the lamination of Polytetrafluoroethylene (PTFE) films, has higher requirements on equipment and process conditions, high cost and great influence on the softness and drapability of fabrics. 3) The coating finishing is the most common water-repellent and waterproof finishing means, but the finishing process causes certain pollution to the environment, and the finishing effect has poor durability and low fastness. 4) The general procedures of finishing by a fluorocarbon padding method are that a finishing agent is attached or grafted to the surface of fabric fibers through padding and drying. Aiming at the defects of the traditional water-repellent and oil-repellent finishing method, the third generation of organosilicon softener, namely the modified organosilicon softener, is developed in the later period of the 70 s. The fabric finished by the amino silicone oil has excellent softness, good smooth feeling and good durability, but has poor hygroscopicity and is easy to yellow. The polyether modified silicone oil has good water solubility, does not need emulsification when in use, and the finished fabric is soft and comfortable, has certain water absorption, antistatic property and antifouling property, but has poor durability because of no reactive group in the molecular structure. The ternary block silicone oil developed by Anqiufeng team of Shanxi university of science and technology solves the three problems of softness, hydrophilicity and adhesive force of polyether modified silicone oil, can endow fabrics with soft, smooth, fluffy and other handfeels, but cannot meet the waterproof and oilproof requirements of certain special occasions.
The fluorosilicone polymer is an ideal fabric finishing agent and has various performances of hydrophilicity, oil repellency, static resistance, easy decontamination and the like. At present, the fluorine-containing monomers frequently used for synthesizing the fluorine-silicon polymer mainly comprise methyl-fluoroalkyl acrylate, fluoroalkyl vinyl ether, fluoroolefin and the like. The commonly used silicon-containing compounds mainly comprise monomers such as silicon-containing alkyl acrylates, vinylsilanes and cyclosiloxanes, and polyalkylhydrosiloxane polymers or macromolecules. The general idea for synthesizing the fluorine-containing silicon polymer is as follows: selecting proper fluorine-containing monomer and silicon-containing monomer, and copolymerizing with other acrylate or ethylene monomers; polymerizing a fluorine-containing monomer with a polyalkylhydrosiloxane polymer or a macromolecule; homopolymerizing a fluorine-containing silicon monomer; or fluorine-containing silicon monomer and other siloxane or acrylate.
In a thesis of preparation of silicon fluoride water and oil repellent finishing agent and application research on wool fabric (litting, 2012) of a university of suzhou, octamethylcyclotetrasiloxane (D4) and trifluoropropyl-methylcyclotrisiloxane (D3F) are subjected to emulsion polymerization under the action of an emulsifier to obtain a fluorosilicone finishing agent, but the fluorosilicone finishing agent has no active group and has insufficient binding force on the fabric. In a short-chain fluorine-containing acrylate water and oil repellent finishing agent and application research thereof (Qianhuahong, 2018) in Master thesis of Jiangnan university, four-carbon short-chain 2- (perfluorobutyl) ethyl acrylate is used as a fluorine-containing monomer to prepare a quaternary fluorine-containing acrylate copolymer miniemulsion; but the system lacks a structure with a smooth hand feel. China journal, namely synthesis and performance of core-shell type fluorosilicone soap-free water and oil repellent finishing agent (Guangzhou chemical engineering, li Chi et al, 2020, vol.48, no. 18, pages 43 to 47), adopts Lauryl Methacrylate (LMA) and Methyl Methacrylate (MMA) as core monomers and dodecafluoro heptyl methacrylate (G04), vinyltriethoxysilane (KH-151) and LMA as shell monomers, and adopts a soap-free emulsion polymerization technology to prepare the core-shell type fluorosilicone acrylate emulsion, so that the core-shell type fluorosilicone acrylate emulsion has good waterproof performance, but the fabric has no hand feeling, which affects actual wearing.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a water-repellent and oil-repellent fabric finishing agent, and the fabric treated by the finishing agent has hydrophobic and oleophobic performances and smooth hand feeling, and can adjust the hand feeling style of the fabric and increase the washability; the invention also provides a preparation method of the composition, which is scientific, reasonable, simple and feasible.
In order to achieve the purpose, the invention adopts the following technical scheme:
a water-repellent and oil-repellent fabric finishing agent has a molecular structure as follows:
NH 2 CH(CH 3 )CH 2 -[OCH(CH 3 )CH 2 ] x -[OCH 2 CH 2 ] y -[OCH 2 CH(CH 3 )] z NH-{[CF 2 CF 2 O] n -[CF 2 O] m } a -{[-(CH 3 ) 2 SiO] q Si(CH 3 ) 2 -} b -NHCH(CH 3 )CH 2 -[OCH(CH 3 )CH 2 ] x -[OCH 2 CH 2 ] y -[OCH 2 CH(CH 3 )] z NH 2 ，
wherein:
0≤x≤10，0≤y≤50，0<z≤10；
n is 0 or an integer of 10 to 30; m is 0 or an integer of 10 to 30; and m and n are not 0 at the same time;
a is an integer of 1 to 10; b is an integer of 1 to 10; q is an integer of 50 to 150. Preferably, 0. Ltoreq. X.ltoreq.6, 0. Ltoreq. Y <40,0< -z.ltoreq.6.
Preferably, 9 ≦ y <40,3 yarn-woven fabric x + z ≦ 6 or x =0,y =0,2 yarn-woven fabric 6.
Further preferably, y ≈ 9,x + z =3.6, or y ≈ 12.5,x + z =6, or y ≈ 39,x + z =6, or x =0,y =0,z ≈ 2.7 or 5.7.
Preferably, the number average molecular weight of the water-repellent and oil-repellent fabric finishing agent is 10000 to 30000, and the amine value can be determined according to the number average molecular weight of the finishing agent because the number of primary amino groups is two terminal groups; the amine value ranges from 0.06 to 0.08mmol/g.
Preferably, m is an integer of 15 to 25, n is an integer of 15 to 25, and further preferably, n is m =1 to 10.
Preferably, a = integers from 3 to 10, b = integers from 3 to 10, and q = integers from 100 to 150; further preferably, a: b =0.5 to 2.
The invention also provides a preparation method of the water-repellent and oil-repellent fabric finishing agent, which comprises the following steps:
(1) Mixing double-end hydroxyl silicone oil and double-end hydroxyl perfluoropolyether alcohol, adding a solvent, heating to carry out dehydration condensation reaction to obtain a perfluoropolyether-silicone oil chain segment with active hydroxyl at two ends;
(2) Adding polyether amine, and carrying out condensation reaction on active hydroxyl and amino under the heating condition to obtain the water-repellent and oil-repellent fabric finishing agent.
The water-repellent and oil-repellent fabric finishing agent is an amino-terminated block fluorosilicone finishing agent, the molecular formula structure of the water-repellent and oil-repellent fabric finishing agent is schematic, and two amino groups at two ends of polyether amine are close in property and can be subjected to condensation reaction with any active hydroxyl of a perfluoropolyether-silicone oil chain segment.
The invention takes double-end hydroxyl silicone oil, double-end hydroxyl perfluoropolyether alcohol and polyether amine as raw materials to carry out dehydration condensation reaction to obtain the silicone oil-perfluoropolyether-polyether amine block compound. The Si-O-Si chain segment in the molecular structure of the finishing agent can rotate in a large angle to provide the softening performance for the finishing agent, the perfluoropolyether chain segment can provide the hydrophobic and oleophobic performance and the smooth performance for the finishing agent, and the hand feeling style of the treated fabric can be adjusted by adjusting the molecular weight and the group distribution of the organosilicon chain and the perfluoropolyether chain. The amino group can be tightly combined with the hydroxyl group on the surface of the fabric, so that the finishing agent is firmly fixed on the surface of the fabric, and the washability of the finishing agent is improved. Adjusting the molecular weight by adjusting the ratio of a to b, wherein the larger a is, the more waterproof the treated fabric is, and the fabric has smooth feeling; the larger b, the softer the treated fabric, but insufficient water repellency and a greasy feel. The distribution of groups can be controlled by using different types of perfluoropolyether alcohols and polyetheramines, -CF of the perfluoropolyether alcohols 2 CF 2 O-and-CF 2 Two segments of O-, -CF 2 The more, the better the waterproofing effect is exhibited.
Preferably, in the step (1), the molar ratio of the hydroxyl-terminated silicone oil to the hydroxyl-terminated perfluoropolyether alcohol is 1. Different ratios, different product molecular weights and different structures. When the hydroxyl-terminated silicone oil: when the double-end hydroxyl perfluoropolyether alcohol = 1; when the hydroxyl-terminated silicone oil: when double-end hydroxyl perfluoropolyether alcohol =1, the product is ABA type, and the molecular weight is 2A + B; when the hydroxyl-terminated silicone oil: and when the double-end hydroxyl perfluoropolyether alcohol =1, the product is AB type. When the hydroxyl-terminated silicone oil: when the double-end hydroxyl perfluoropolyether alcohol is in other proportion, the structure of the product is between the three.
Preferably, in the step (1), the solvent is isopropanol, and the dosage of the isopropanol is 8 to 20 times of the mass of the reaction product. More preferably 8 to 13 times. The reactant refers to the sum of double-end hydroxyl silicone oil, double-end hydroxyl perfluoropolyether alcohol and polyether amine.
The hydroxyl-terminated siliconOil of the formula HO [ (CH) 3 ) 2 SiO] q Si(CH 3 ) 2 -OH, which is a linear polymer taking a repeated siloxane bond as a main chain and methyl as a side group and terminated by hydroxyl, wherein q is an integer of 50 to 150.
The structural formula of the double-end hydroxyl perfluoropolyether alcohol is OH [ CF ] 2 CF 2 O] n -[CF 2 O] m H, m and n are respectively an integer of 10 to 30 independently, or one of the integers is 0. Perfluoropolyether alcohols with different specifications can be selected, and the proportional relation of m and n can be adjusted. The perfluoropolyether alcohol can also be selected based on molecular weight, with the perfluoropolyether alcohol having a reduced molecular weight and the product having reduced oil and water repellency. In the present invention, suitable double-terminal hydroxyl perfluoropolyether alcohols have a molecular weight of 1600 to 4000.
Preferably, in the step (1), the temperature of the dehydration condensation reaction is 70 to 100 ℃, and the condensation reaction time is 2 to 3 hours.
In the step (2), the polyether amine (PEA) is a bifunctional polymer with a main chain of a polyether structure and an active functional group at the tail end of an amino group, and the molecular weight is 230 to 2000.
Further preferably, in the step (2), the polyether amine is selected from one or more of ED600, ED900, D230, ED2003 or D400.
The structural general formulas of ED600, ED900 and ED2003 are as follows:
NH 2 CH(CH 3 )CH 2 -[OCH(CH 3 )CH 2 ]x-[OCH 2 CH 2 ]y-[OCH 2 CH(CH 3 )]z-NH 2 ，
the ED600: y ≈ 9, (x + z) =3.6; the amine value is 3.2-3.5 mmol/g;
ED900: y ≈ 12.5, (x + z) =6; the amine value is 1.8-2.25 mmol/g;
ED2003: y ≈ 39, (x + z) =6; the amine value is 0.9-1.05 mmol/g.
The structural general formulas of D230 and D400 are as follows: NH 2 CH(CH 3 )CH 2 [OCH 2 CH(CH 3 )]zNH 2 ，
D230: the number average molecular weight Mn is about 230; d400: the number-average molecular weight Mn is about 400.
Part of the polyether amine contains two chain members, PO and EO, PO: EO is selected according to different specifications of polyether amine and has different proportions. The PO chain link is-OCH (CH) 3 )CH 2 -and/or-OCH 2 CH(CH 3 ) -, is a branched structure; the EO chain link is-OCH 2 CH 2 -. The PO chain links provide fluffy feeling for the fabric, and the EO chain links can improve the smooth feeling of the fabric and can be adjusted according to requirements. The different types of polyetheramines EO/PO differ, and therefore the treated fabrics exhibit different hand. In the invention, the chain segment providing smooth feeling is mainly perfluoropolyether, and EO chain segment in the polyether amine can play a certain auxiliary role.
Preferably, in the step (2), the molar ratio of the polyether amine to the hydroxyl-terminated silicone oil is 0.5 to 1.2. More preferably 1 to 1.2.
Preferably, in the step (2), the heating condition is 70 to 100 ℃, and the condensation reaction time is 2 to 3 hours.
The invention also provides a stock solution of the water-repellent and oil-repellent fabric finishing agent, which can be stably stored, wherein the obtained water-repellent and oil-repellent fabric finishing agent is diluted by isopropanol, and the mass content of the water-repellent and oil-repellent fabric finishing agent in the stock solution is 20-70%.
Compared with the prior art, one or more technical schemes provided by the embodiment of the invention at least have the following beneficial effects:
1. according to the invention, the silicone oil chain segment, the perfluoropolyether chain segment and the polyether amine chain segment are combined into a block structure, so that the finishing agent with good water and oil repellency is obtained. The Si-O-Si main chain of the silicone oil has longer bond length than C-C bond, large bond angle and high bond energy, and the characteristics determine that the silicone oil chain segment has high stability and can improve the softness of fabrics. The perfluoropolyether chain segment has the properties of hydrophobicity and oleophobicity, and the fabric treated by the finishing agent containing the perfluoropolyether chain segment has the characteristics of water repellency, oil repellency and smoothness. The polyether amine is composed of PO chain links and EO chain links, the PO chain links provide fluffy feeling for the fabric, the EO chain links improve the smooth feeling of the fabric, and the polyether amine can be adjusted according to requirements. The invention can adjust the hand feeling style of the fabric by adjusting the molecular weight and the group distribution of the organic silicon chain and the perfluoropolyether chain.
2. In the invention, the perfluoro polyether alcohol, the silicone oil and the polyether amine are firstly prepared into the block polymer and used for finishing the fabric, and the excellent smooth hand feeling is shown. This is due to the fact that the perfluoropolyether alcohols have a formula of-CF 2 O-and-CF 2 CF 2 O-two chain links, and the proportion and the number can be adjusted, and because all H atoms are replaced by F atoms, the shielding effect of the F atoms ensures that the integral surface tension is extremely low, and the water-repellent oil-repellent material is a good water-repellent material. The perfluoropolyether chain is free to flex and provides a smooth feel when used in fabric finishing. In addition, the LD56 value of the perfluoropolyether in an oral acute toxicity test of mice is high, no accumulation is generated in organisms, and the decomposition temperature is as high as 400 ℃.
3. In the present invention, the-NH at the end of the textile finish 2 Is reactive amino, and reacts with reactive OH on the surface of the fabric under the heating condition, so that the finishing agent is firmly fixed on the surface of the fabric, and the water washing resistance is strong.
4. The water contact angle of the fiber fabric treated by the finishing agent of the invention is more than 140 degrees, and the contact angles of 3 kinds of oil (white mineral oil, n-tetradecane and n-decane) are all more than 90 degrees o (ii) a The fabric has soft and smooth hand feeling through the evaluation of hand feeling style.
5. The preparation method is scientific, reasonable, simple and feasible.
Drawings
FIG. 1 is a water contact angle test chart of the sample of example 1;
FIG. 2 is a test chart of No. 3 oil contact angle of the sample of example 3.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention. The raw materials used in the examples of the present invention are all available commercially.
Example 1
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 100g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-neck bottle, adding 3000g of isopropanol serving as a solvent, heating to 100 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain perfluoropolyether-silicone oil alternating chain segments with active hydroxyl groups at two ends;
15g (-NH) 2 Content of 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was added for dilution.
Example 2
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 200g (hydroxyl content is 0.1 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-neck bottle, adding 3000g of isopropanol serving as a solvent, heating to 70 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain perfluoropolyether-silicone oil chain segments with active hydroxyl groups at two ends;
15g (-NH) of polyetheramine ED600 (EO: PO =5 2 Content of 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 2 hours at 100 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was additionally added for dilution.
Example 3
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 50g (hydroxyl content is 0.025 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-mouth bottle, adding 3000g of isopropanol serving as a solvent, heating to 80 ℃, and carrying out dehydration condensation reaction for 3 hours to obtain a perfluoropolyether-silicone oil chain segment with active hydroxyl groups at two ends;
15g (-NH) 2 Content 0.05 mol)Adding the mixture into a three-neck bottle, and continuously reacting for 2 hours at 70 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was additionally added for dilution.
Example 4
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 100g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-neck bottle, adding 3000g of isopropanol serving as a solvent, heating to 100 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain perfluoropolyether-silicone oil alternating chain segments with active hydroxyl groups at two ends;
the polyether amine ED600 (EO: PO =5 2 Content of 0.06 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was added for dilution.
Example 5
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 100g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-mouth bottle, adding 3000g of isopropanol serving as a solvent, heating to 100 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain a perfluoropolyether-silicone oil alternating chain segment with active hydroxyl groups at two ends;
the polyether amine ED600 (EO: PO =5 2 Content of 0.025 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was additionally added for dilution.
Example 6
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 100g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-mouth bottle, adding 3000g of isopropanol serving as a solvent, heating to 80 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain a perfluoropolyether-silicone oil chain segment with active hydroxyl groups at two ends;
the polyether amine ED900 (EO: PO =25, 12,mn = 900) was charged with 22.5g (-NH) 2 Content of 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was additionally added for dilution.
Example 7
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 100g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-mouth bottle, adding 3000g of isopropanol serving as a solvent, heating to 80 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain a perfluoropolyether-silicone oil chain segment with active hydroxyl groups at two ends;
5.75g (-NH) of polyetheramine D230 (PO only, mn = 230) 2 Content of 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was additionally added for dilution.
Example 8
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 100g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-mouth bottle, adding 3000g of isopropanol serving as a solvent, heating to 80 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain a perfluoropolyether-silicone oil chain segment with active hydroxyl groups at two ends;
a polyether amine ED2003 (EO: PO =39 2 Content of 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was additionally added for dilution.
Example 9
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 40g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 1600) into a three-neck bottle, adding 3000g of isopropanol serving as a solvent, heating to 80 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain perfluoropolyether-silicone oil alternating chain segments with active hydroxyl groups at two ends;
15g (-NH) of polyetheramine ED600 (EO: PO =5 2 Content of 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was additionally added for dilution.
Example 10
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 57.5g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 2300) into a three-neck flask, adding 3000g of isopropanol serving as a solvent, heating to 80 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain perfluoropolyether-silicone oil alternating chain segments with active hydroxyl groups at two ends;
15g (-NH) 2 Content of 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was added for dilution.
Example 11
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 125.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxy silicone oil (Mn = 5000) and 100g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-neck flask, adding 3000g of isopropanol serving as a solvent, heating to 80 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain a perfluoropolyether-silicone oil alternating chain segment with active hydroxyl groups at two ends;
15g (-NH) 2 Content 0.05 mol) into a three-necked flask, and continuing the reaction at 80 ℃ for 3h, obtaining the amino-terminated block fluorine-silicon finishing agent, namely the water-repellent and oil-repellent fabric finishing agent. The silicone oil chain segment provides more excellent softness performance to the fabric, the longer the silicone oil chain segment, the better the softness, and vice versa.
For storage stability, 200g of isopropanol was added for dilution.
Example 12
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 250g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 10000) and 100g (hydroxyl content is 0.05 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-neck bottle, adding 3000g of isopropanol serving as a solvent, heating to 80 ℃, carrying out dehydration condensation reaction for 2 hours, and obtaining a perfluoropolyether-silicone oil alternate chain segment with active hydroxyl groups at two ends;
15g (-NH) of polyetheramine ED600 (EO: PO =5 2 Content of 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃ to obtain the amino-terminated block fluorosilicone finishing agent, namely the water-repellent and oil-repellent fabric finishing agent.
For storage stability, 200g of isopropanol was added for dilution.
Comparative example 1
A preparation method of a fabric finishing agent comprises the steps of adding 250g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 10000) and 5.7g of allyl glycidyl ether into a three-mouth bottle, adding 0.5g of Pt catalyst (1% chloroplatinic acid isopropanol solution) and 3000g of isopropanol solvent, heating to 80 ℃, and carrying out dehydration condensation reaction to obtain a perfluoropolyether-silicone oil alternating chain segment with active hydroxyl groups at two ends;
15g (-NH) of polyetheramine ED600 (EO: PO = 5) 2 Content 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃, thus obtaining the amino-terminated block silicon-ether finishing agent.
For storage stability, 200g of isopropanol can be added for dilution.
Comparative example 2
A preparation method of a water-repellent and oil-repellent fabric finishing agent comprises the steps of adding 200.0g (hydroxyl content is 0.05 mol) of alpha, omega-hydroxyl silicone oil (Mn = 8000) and 20g (hydroxyl content is 0.01 mol) of double-end hydroxyl perfluoropolyether alcohol (Mn = 4000) into a three-mouth bottle, adding 3000g of isopropanol serving as a solvent, heating to 100 ℃, and carrying out dehydration condensation reaction for 2 hours to obtain a perfluoropolyether-silicone oil alternating chain segment with active hydroxyl groups at two ends;
the polyether amine ED600 (EO: PO = 5) 15g (-NH 2 Content of 0.05 mol) is added into a three-necked bottle, and the reaction is continued for 3 hours at 80 ℃, thus obtaining the amino-terminated block fluorosilicone finishing agent.
For storage stability, 200g of isopropanol can be added for dilution.
The finishes prepared in the examples and comparative examples were tested for properties:
1.5g of the amino-terminated block fluorosilicone finishing agent obtained in the examples or the comparative examples is weighed in a beaker, 100.0g of deionized water is added for dilution to prepare working bath liquid, then the cotton fabric (pure cotton gray fabric) with a certain size cut in advance is placed in the working bath liquid, the cotton fabric is soaked and rolled twice on a small rolling mill in a laboratory (the rolling residual ratio is 80 percent), and finally the fabric sample is baked for 3min at 160 ℃.
The detection method comprises the following steps:
(1) Water contact angle: a water contact angle determinator was used.
Oil contact angle: AATCC standard liquid systems were used, see table 1 in particular:
TABLE 1AATCC standard fluid system
The contact angle test results are shown in table 2:
TABLE 2 Water and oil contact Angle test results
(2) And (3) hand feeling test: the comprehensive hand feeling is divided into 1-5 grades from the worst to the best, 5 experts for evaluating the hand feeling style evaluate the hand feeling of the fabric from three dimensions of smoothness, fluffiness and softness respectively, and the comprehensive average grade is the final conclusion. The results of the tests are shown in Table 3:
TABLE 3 hand feeling evaluation results
FIG. 1 is a water contact angle test chart of the sample of example 1; FIG. 2 is a test chart of No. 3 oil contact angle of the sample of example 3. Through a plurality of examples and comparative examples provided by the invention, it can be seen that the perfluoropolyether alcohol is used for a fabric finishing agent, the water-repellent effect and the smoothness of fabrics can be improved, and the more the perfluoropolyether chain segments are, the larger the molecular weight is, and the better the water-repellent and oil-repellent effect is. The silicone oil chain segment provides soft hand feeling for the fabric, and the more the silicone oil chain segment is, the larger the molecular weight is, and the more obvious the softness is. The amino introduced by the polyether amine can be combined with the active hydroxyl of the fabric, so that the binding force of the finishing agent and the fabric is improved, and good water resistance and sufficient hand feeling are embodied. The proportion of the silicone oil chain segment to the perfluoropolyether chain segment is proper in the range of 1 to 2, and when the proportion exceeds the range, the molecular structure of the product is not uniform, and the finishing of the fabric by using the product has influence on the hydrophobic and oleophobic properties and the hand feeling. In addition, PO chain segments of the polyether amine structure are increased, the fluffy feeling of the fabric is increased, the EO chain segments are increased to a certain degree, and the smooth feeling of the fabric is enhanced.
Claims (4)
1. A preparation method of a water-repellent and oil-repellent fabric finishing agent is characterized by comprising the following steps:
(1) Mixing double-end hydroxyl silicone oil and double-end hydroxyl perfluoropolyether alcohol, adding a solvent, heating to perform a dehydration condensation reaction to obtain a perfluoropolyether-silicone oil chain segment with active hydroxyl groups at two ends, wherein the molar ratio of the double-end hydroxyl silicone oil to the double-end hydroxyl perfluoropolyether alcohol is 1 to 0.5-2;
(2) Adding polyether amine, and performing condensation reaction on active hydroxyl and amino under the heating condition to obtain the water-repellent and oil-repellent fabric finishing agent, wherein the water-repellent and oil-repellent fabric finishing agent is an amino-terminated block fluorosilicone finishing agent.
2. The method for producing a water-and oil-repellent fabric finishing agent according to claim 1, characterized in that in the step (1), the temperature of the dehydration condensation reaction is 70 to 100 ℃ and the condensation reaction time is 2 to 3 hours.
3. The process for producing a water-and oil-repellent fabric finishing agent according to claim 1, characterized in that step (2) satisfies at least one of the following conditions:
the polyether amine is a bifunctional polymer with a main chain of a polyether structure and an active functional group at the tail end of an amino group, and the molecular weight is 230-2000;
(ii) the molar ratio of the polyether amine to the hydroxyl-terminated silicone oil is 0.5 to 1.2;
(iii) the heating temperature is 70 to 100 ℃ and the condensation reaction time is 2 to 3 hours.
4. A stock solution of a water-repellent and oil-repellent fabric finishing agent is characterized in that the water-repellent and oil-repellent fabric finishing agent prepared by the method of any one of claims 1 to 3 is diluted with isopropanol, and the content of the water-repellent and oil-repellent fabric finishing agent in the stock solution is 20 to 70 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211306442.XA CN115368575B (en) | 2022-10-25 | 2022-10-25 | Water-repellent and oil-repellent fabric finishing agent, finishing agent stock solution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211306442.XA CN115368575B (en) | 2022-10-25 | 2022-10-25 | Water-repellent and oil-repellent fabric finishing agent, finishing agent stock solution and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115368575A CN115368575A (en) | 2022-11-22 |
| CN115368575B true CN115368575B (en) | 2023-01-13 |
Family
ID=84072779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211306442.XA Active CN115368575B (en) | 2022-10-25 | 2022-10-25 | Water-repellent and oil-repellent fabric finishing agent, finishing agent stock solution and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115368575B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004530A (en) * | 2021-04-12 | 2021-06-22 | 江苏尼美达科技有限公司 | Multi-component copolymer block silicone oil and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2691118B1 (en) * | 2011-03-31 | 2019-05-01 | Schäfer, Konstanze | Perfluorinated compounds for the non-viral transfer of nucleic acids |
| CN108239519B (en) * | 2018-01-02 | 2020-11-27 | 深圳市广业电子科技有限公司 | Fast-curing one-component room-temperature-curing organic silicon composition |
| CN110183822A (en) * | 2019-06-25 | 2019-08-30 | 苏州宇希新材料科技有限公司 | A kind of preparation method of high-toughness epoxy resin composition |
| CN111393654B (en) * | 2020-04-29 | 2021-10-15 | 杭州美高华颐化工有限公司 | Preparation method of multifunctional nylon block silicone oil |
| CN114957646B (en) * | 2022-04-06 | 2024-04-16 | 东莞泰岳先进材料有限公司 | Perfluoro polyether amino compound and preparation method and application thereof |
-
2022
- 2022-10-25 CN CN202211306442.XA patent/CN115368575B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004530A (en) * | 2021-04-12 | 2021-06-22 | 江苏尼美达科技有限公司 | Multi-component copolymer block silicone oil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115368575A (en) | 2022-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107129578B (en) | Preparation method of amino modified silicone oil finishing agent with net structure | |
| EP1682615B1 (en) | Mixture of fluorinated polyethers and use thereof as surfactant | |
| CN107814941B (en) | Microwave preparation method of smooth quaternary ammonium block organic silicon polymer | |
| CN109575294B (en) | V-shaped polydimethylsiloxane polyoxyethylene ether monoacrylate and preparation method thereof | |
| CN105671970B (en) | No fluoro water proofing agent used for textiles and preparation method thereof | |
| CN102159605B (en) | Aqueous polymer dispersion composition and surface treatment agent | |
| CN104892850B (en) | A kind of preparation method of lateral chain fluorine-containing waterborne polyurethane | |
| WO2006121171A1 (en) | Fluorosilicones and fluorine- and silicon-containing surface treatment agent | |
| CN102159606B (en) | Fluorosilicone polymers and surface treatment agent | |
| WO1992019663A1 (en) | Fluoroacrylate monomers and polymers, processes for preparing the same and their use | |
| CN101981248A (en) | Dispersion of fluorosilicones and fluorine- and silicon-containing surface treatment agent | |
| EP2501850A1 (en) | Fluoropolymers and treatment agent | |
| CN112029032B (en) | Preparation method of durable fabric waterproof finishing agent and product thereof | |
| EP2501851A1 (en) | Fluoropolymers and surface treatment agent | |
| CN102164976A (en) | Fluorosilicones and surface treatment agent | |
| TWI781360B (en) | Water repellent softener | |
| CN104558618A (en) | Block modified silicone as well as preparation method and application thereof | |
| CN104452453A (en) | Water-based waterproof oil-proof agent for special paper, and preparation method thereof | |
| CN115368575B (en) | Water-repellent and oil-repellent fabric finishing agent, finishing agent stock solution and preparation method thereof | |
| CN106835719B (en) | A kind of betaine type amphoteric silicone softening agent and preparation method thereof | |
| EP1454929B1 (en) | Fluorinated polyether monomer, polymer formed therefrom, and surface-treating agent | |
| CN102505495A (en) | High-elastic smooth silicon softener and preparation method and application thereof | |
| CN101747511B (en) | Polysiloxane containing fluorine and application thereof | |
| CN113957722A (en) | Environment-friendly fluorine-free waterproof agent and preparation method thereof | |
| CN112745507A (en) | Fluorine-containing silicone oil, 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |