CN111286987B - Organic silicon quaternary ammonium salt fabric finishing agent based on block silicone oil and preparation method thereof - Google Patents
Organic silicon quaternary ammonium salt fabric finishing agent based on block silicone oil and preparation method thereof Download PDFInfo
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- CN111286987B CN111286987B CN202010111980.8A CN202010111980A CN111286987B CN 111286987 B CN111286987 B CN 111286987B CN 202010111980 A CN202010111980 A CN 202010111980A CN 111286987 B CN111286987 B CN 111286987B
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- 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
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
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- 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
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- 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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- 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
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- 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
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- Engineering & Computer Science (AREA)
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Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to an organosilicon quaternary ammonium salt fabric finishing agent based on block silicone oil and a preparation method thereof; the method comprises the following specific steps: adding epichlorohydrin into ternary block copolymerized silicone oil for heating reaction to obtain a block silicone oil intermediate containing a chlorohydrocarbon branched chain; and then adding triethylamine or triethanolamine, and continuously heating and reacting for a period of time to obtain the organic silicon quaternary ammonium salt fabric finishing agent based on the block silicone oil. The finishing agent has good flexibility, high stability and small influence on whiteness and hydrophilicity, and has a quaternary ammonium salt structure and good antibacterial ability; moreover, the fabric has excellent antibacterial performance, can also have other good effects such as softness, smoothness, elasticity and the like, and has good practical value and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to an organic silicon quaternary ammonium salt fabric finishing agent based on block silicone oil and a preparation method thereof.
Background
With the improvement of living standard, the requirements of people on environmental sanitation are higher and higher, the self-protection consciousness is increasingly strengthened, and the comfort and health care functions of clothes are increasingly emphasized. A large number of various microorganisms are present on garments and fabrics. Although most of these microorganisms are nonpathogenic, their proliferation can cause abnormal irritation of human skin. Sweat, sebum and fallen scraps of the epidermis of the human skin provide proper conditions for bacterial reproduction; under the action of bacteria, the bacteria is easy to decompose to generate odor, so as to form mould and induce skin diseases and infectious diseases. Therefore, the development of antibacterial and deodorant processing technology and antibacterial and deodorant finishing agent for textiles is increasing (Zhou Jian Hua, in the Tao. Synthesis of polysiloxane quaternary ammonium salt antibacterial softening finishing agent. Organosilicon material, 2006,20 (5): 238-242).
The organosilicon quaternary ammonium salt fabric finishing agent perfectly combines quaternary ammonium salt and polysiloxane, combines cationic groups with sterilization performance on the surface of fibers by chemical bonds, attracts bacteria, fungi, yeasts and the like with negative charges, and leads the bacteria, the fungi, the yeasts and the like to be subjected to contact death so as to play the roles of sterilization and bacteriostasis. The antibacterial finishing agent belongs to a non-dissolution type, is firmly and durably combined with fiber, has obvious antibacterial effect, and is safe and reliable to human bodies (Zhaojie, anqifeng, plum, and the like, application of organic silicon in the antibacterial finishing agent, chemical development, 2014,26 (2): 310-319). However, the existing organosilicon quaternary ammonium salt fabric finishing agent has the defects of difficult synthesis, single performance and the like. Therefore, it is necessary to research a simple method for preparing a fabric finishing agent, which can provide antibacterial property and also can endow fabric with properties such as softness, smoothness and elasticity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a block silicone oil-based organosilicon quaternary ammonium salt fabric finishing agent and a preparation method thereof to solve the problems.
In order to achieve the technical purpose, the technical scheme adopted by the invention comprises the following steps:
the invention firstly provides an organosilicon quaternary ammonium salt fabric finishing agent based on block silicone oil, and the structural formula of the organosilicon quaternary ammonium salt fabric finishing agent is as follows:
wherein R = -H or-OH
n，m＝50～100；a，b＝5～15；
The invention also provides a preparation method of the organic silicon quaternary ammonium salt fabric finishing agent based on the block silicone oil, which comprises the following two steps of reaction in one pot:
wherein R = -H or-OH
n,m＝50～100；a,b＝5～15
Adding a certain amount of epichlorohydrin into ternary block copolymerized silicone oil, carrying out a first heating reaction, and reacting for a period of time to obtain a block silicone oil intermediate containing a chlorohydrocarbon branched chain; then adding a certain amount of triethylamine or triethanolamine, carrying out a second heating reaction, and reacting for a period of time to obtain the organic silicon quaternary ammonium salt fabric finishing agent based on the block silicone oil.
The molecular weight of the ternary block copolymerized silicone oil is 6000-20000.
The mass ratio of the ternary block copolymerized silicone oil to the epichlorohydrin to the triethylamine is 100:1 to 3:1 to 3.
The mass ratio of the ternary block copolymerized silicone oil, the epichlorohydrin to the triethanolamine is 100:1 to 3:1.5 to 4.5.
The temperature of the first heating reaction is 80-110 ℃, and the reaction time is 0.5-3h.
The temperature of the second heating reaction is 90-120 ℃, and the reaction time is 1-4h.
The invention has the beneficial effects that:
the organosilicon quaternary ammonium salt prepared by the invention is a cationic surfactant which is most widely applied at present, can be used as a clothes antibacterial agent, a softening agent and an antistatic agent, and is also applied to the fields of cosmetics, leather and the like. The block polyether amino silicone oil has a good softening finishing effect as a fabric finishing agent, and the organic silicon quaternary ammonium salt fabric finishing agent prepared by quaternizing and improving the block polyether amino silicone oil endows fabrics with excellent antibacterial performance, can endow fabrics with other good effects such as softness, smoothness, elasticity and the like, and has a good practical value.
Detailed Description
The invention will be further understood by reference to the following examples, which are not intended to limit the invention thereto.
Example 1:
30g of ternary block copolymerization silicone oil with the molecular weight of about 11000 and 0.3g of epoxy chloropropane are added into a 100mL three-neck flask, stirred and heated to 105 ℃, after reaction for 1.0 hour, 0.45g of triethanolamine is added into the flask, stirring reaction is continued at 110 ℃ for 2 hours, and the product, namely the organosilicon quaternary ammonium salt fabric finishing agent I is obtained after the reaction is finished.
And (3) an emulsification process: and (3) pouring 30g of the product into a 250mL beaker, adding 10 drops of acetic acid, slowly adding 70g of 0.1% acetic acid solution dropwise, and quickly stirring until the solution is clear to obtain the organosilicon quaternary ammonium salt fabric finishing agent I emulsion with the content of 30%.
Example 2:
30g of ternary block copolymerized silicone oil with the molecular weight of about 11000 and 0.3g of epoxy chloropropane are added into a 100mL three-neck flask, stirred and heated to about 95 ℃ for reaction for 2.5h, and a ring-opening addition reaction product is obtained after the reaction is finished. And continuously adding 0.25g of triethylamine into the bottle, continuously stirring and reacting for 1.5h at 120 ℃, and obtaining the product organosilicon quaternary ammonium salt finishing agent II after the reaction is finished.
And (3) an emulsification process: and pouring 30g of the product into a 250mL beaker, adding 10 drops of acetic acid, slowly adding 70g of 0.1% acetic acid solution dropwise, and quickly stirring until the solution is clear to obtain the organosilicon quaternary ammonium salt fabric finishing agent II emulsion with the content of 30%.
Example 3:
30g of ternary block copolymerized silicone oil with the molecular weight of 6000 and 0.5g of epoxy chloropropane are added into a 100mL three-neck flask, stirred and heated to about 100 ℃ for reaction for 2.0h, then 0.7g of triethanolamine is added into the flask, the stirring reaction is continued at 90 ℃ for 4h, and the product organosilicon quaternary ammonium salt fabric finishing agent III is obtained after the reaction is finished.
And (3) an emulsification process: and pouring 30g of the product into a 250mL beaker, adding 10 drops of acetic acid, slowly adding 70g of 0.1% acetic acid solution dropwise, and quickly stirring until the solution is clear to obtain the organosilicon quaternary ammonium salt fabric finishing agent III emulsion with the content of 30%.
Example 4:
adding 30g of ternary block copolymerized silicone oil with the molecular weight of about 8000 and 0.4g of epoxy chloropropane into a 100mL three-neck flask, stirring, heating to 80 ℃, reacting for 3h, and obtaining a ring-opening addition reaction product after the reaction is finished; and continuously adding 0.35g of triethylamine into the bottle, continuously stirring at 100 ℃ for reacting for 2.5 hours to obtain a product, namely the organosilicon quaternary ammonium salt finishing agent IV.
And (3) an emulsification process: and pouring 30g of the product into a 250mL beaker, adding 10 drops of acetic acid, slowly adding 70g of 0.1% acetic acid solution dropwise, and quickly stirring until the solution is clear to obtain the organosilicon quaternary ammonium salt fabric finishing agent IV emulsion with the content of 30%.
The application process of the organosilicon quaternary ammonium salt fabric finishing agent comprises the following steps:
treating the fabric: polyester cotton twill;
the treatment process comprises the following steps: 30g/L;
one-dip one-roll (rolling residual rate: 70%) → oven setting (150 ℃x60 s) → cooling and moisture regaining → performance evaluation:
and (4) performance testing:
hand feeling: a multi-person hand touch evaluation method is adopted, the grade is 1-5, and the larger the numerical value is, the softer the numerical value is; whiteness: the higher the difference value with the original cloth is, the better the yellowing resistance is; hydrophilicity: a drop of water was dropped from a height using a standard dropper onto the fabric surface and the time required for complete wetting was recorded. The test results are given in the following table:
the acid resistance, alkali resistance, salt resistance and shear resistance are shown in the following table:
the data show that the organic silicon quaternary ammonium salt fabric finishing agent based on the block silicone oil has excellent hand feeling, good whiteness and hydrophilicity, good acid resistance, alkali resistance, salt resistance and shearing resistance, and the quaternary ammonium salt structure has good antibacterial capability and wide application prospect.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (1)
1. The preparation method of the organic silicon quaternary ammonium salt fabric finishing agent based on the block silicone oil is characterized by comprising the following specific steps:
adding a certain amount of epoxy chloropropane into the ternary block copolymerized silicone oil, carrying out a first heating reaction, and reacting for 1-3h at the temperature of 80-105 ℃ to obtain a block silicone oil intermediate containing a chlorinated hydrocarbon branched chain; then adding a certain amount of triethylamine or triethanolamine, carrying out a second heating reaction, and reacting for 1.5-4h at 100-120 ℃ to obtain the organic silicon quaternary ammonium salt fabric finishing agent based on the block silicone oil;
the molecular weight of the ternary block copolymerized silicone oil is 6000 to 20000;
the mass ratio of the ternary block copolymerized silicone oil to the epichlorohydrin to the triethylamine is 100:1 to 3:1 to 3;
the mass ratio of the ternary block copolymerized silicone oil to the epichlorohydrin to the triethanolamine is 100:1 to 3:1.5 to 4.5;
the structural formula of the organic silicon quaternary ammonium salt fabric finishing agent is as follows:
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| CN111807711B (en) * | 2020-07-24 | 2022-05-13 | 江苏秀强玻璃工艺股份有限公司 | Manufacturing process of super-hydrophilic long-life organosilicon quaternary ammonium salt antibacterial glass |
| CN112409598B (en) * | 2020-11-19 | 2021-06-01 | 广东工业大学 | Bola type organosilicon quaternary ammonium salt, preparation method and application thereof |
| CN115926174B (en) * | 2023-01-03 | 2023-12-05 | 宁波润禾高新材料科技股份有限公司 | Anti-phenolic yellowing hydrophilic polysiloxane material, preparation method and application thereof |
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