CN101608402B - Vegetable oil modified fluoride-containing water repellent finishing agent as well as preparation method and application thereof - Google Patents
Vegetable oil modified fluoride-containing water repellent finishing agent as well as preparation method and application thereof Download PDFInfo
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- CN101608402B CN101608402B CN2009100547794A CN200910054779A CN101608402B CN 101608402 B CN101608402 B CN 101608402B CN 2009100547794 A CN2009100547794 A CN 2009100547794A CN 200910054779 A CN200910054779 A CN 200910054779A CN 101608402 B CN101608402 B CN 101608402B
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- vegetable oil
- finishing agent
- water repellent
- repellent finishing
- containing water
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Abstract
The invention relates to a vegetable oil modified fluoride-containing water repellent finishing agent as well as a preparation method and an application thereof. The preparation comprises: (1) adding hot water and NaOH into the vegetable oil, carrying out water bath heating at 80 DEG C to obtain sodium aliphatate;(2) dissolving the sodium aliphatate with water and adding sulfuric acid for acidification to obtain higher fatty acid; and (3) reacting the higher fatty acid with CF3-(CF2)n-CH2OH at 60 DEG C for 4-8 h to obtain the vegetable oil modified fluoride-containing water repellent finishing agent. The water repellent finishing agent of the invention does not have obvious influence on the air permeability, whiteness and breaking strength of cellulosic fiber; and synthesis process is simple, cost is low, raw material is environment-friendly, and environment pollution is slight.
Description
Technical field
The invention belongs to fluorine-containing water repellent finishing agent and preparation field thereof, particularly relate to a kind of vegetable oil modified fluoride-containing water repellent finishing agent, preparation method and application thereof.
Background technology
Water repellent finish is an importance of finishing functions.Along with continuous progress in science and technology, new fabric water repellent finish technology is constantly adopted by people, and metallic soap class, metal complex, pyridines, methylol compound and silicone based finishing agent are used as the water repellent finish of fabric in succession.
But, water repellent finishing agent in the past is all owing to the harmful effect to fabric feeling, gas permeability, whiteness etc., poor durability and environmental factor etc. are eliminated gradually, thereby people bring into use the Organic fluoride finishing agent of low-surface-energy to come fabric is carried out water and oil repellent finish, the Organic fluoride fabric finishing agent relies on performances such as its good hydrophobic and lyophobic property, gas permeability and washable antifouling and easy decontamination to be shown one's talent, and becomes the main flow of current water-repellent oil-repellent agent.Lining through Organic fluoride arrangement processing is mainly used in civilian and the medical protection lining.
Its good wearability of cellulose fiber denapon is subjected to people's welcome at garment industry, yet reduce through the cellulose fibre hydrophily after the Organic fluoride arrangement, cause fabric to be easy to generate static, the original wearability of cellulose fibre is caused bad influence, and the ecological problem of organic fluorine chemistry product is familiar with by people gradually also.
Because current energy resource shortage, the finishing agent of exploitation living beings is significant.Vegetable oil is a kind of raw material of living beings, aboundresources, nontoxic, ecological, environmental protective, with low cost, and owing to self specific structure has possessed certain water repellency, through modification, after the reaction of fluorine-containing alcohols material, can obtain the good water effect of refusing, can effectively reduce cost, energy savings again.
Summary of the invention
Technical problem to be solved by this invention provides a kind of vegetable oil modified fluoride-containing water repellent finishing agent, preparation method and application thereof, and this water repellent finishing agent can not produce significantly influence to gas permeability, whiteness and the ultimate strength of cellulose fibre; And synthesis technique is simple, cost is low, the raw material environmental protection, and environmental pollution is little.
A kind of vegetable oil modified fluoride-containing water repellent finishing agent of the present invention, chemical structure of general formula is as follows:
R represents the fatty carbon chain of different carbon atoms, n=0,1,2 ... 7, this water repellent finishing agent is by different aliphatic acid and CF in the vegetable oil
3-(CF
2) n-CH
2The mixture that the ester that the OH reaction generates is formed.With the castor oil is example, and castor oil modified fluorine-containing water repellent finishing agent is the mixture that following several ester is formed:
C
6H
13CHOHCH
2CH＝CH(CH
2)
7COOCH
2(CF
2)n-CF
3，
CH
3(CH
2)
7CH＝CH(CH
2)
7COOCH
2(CF
2)n-CF
3，
CH
3(CH
2)
4CH＝CH-CH
2-CH＝CH(CH
2)
7COOCH
2(CF
2)n-CF
3，
CH
3(CH
2)
14COOCH
2(CF
2) n-CF
3, CH
3(CH
2)
16COOCH
2(CF
2) n-CF
3, and
CH
3CH
2(CH＝CHCH
2)
3(CH
2)
6COOCH
2(CF
2)n-CF
3。Its proterties is light yellow to brown yellow transparent liquid.
Described finishing agent is used for the water repellent finish of cellulose fibre, refuses water section and is the long carbochain in the vegetable oil and can significantly reduce the capillary C-F key of cellulose fibre.
The preparation method of a kind of vegetable oil modified fluoride-containing water repellent finishing agent of the present invention comprises:
(1) add hot water (more than 70 ℃) and NaOH in vegetable oil, 80 ℃ of water-bath heating promptly get sodium soap;
(2) with above-mentioned sodium soap water-soluble, add sulfuric acid acidation, promptly get higher fatty acids;
(3) with above-mentioned higher fatty acids and CF
3CH
2OH obtains vegetable oil modified fluoride-containing water repellent finishing agent at 60 ℃ of reaction 4-8h.
Described step (1) vegetable oil is palm oil, castor oil, peanut oil, rapeseed oil, soybean oil, cottonseed wet goods.
Vegetable oil modified fluoride-containing water repellent finishing agent provided by the invention and preparation method have mainly utilized the principle of the characteristic of low surface tension of C-F and saponification, esterification.Different with traditional water repellent finishing agent, vegetable oil modified fluoride-containing water repellent finishing agent is because vegetable oil itself just has certain waterproofing function, and with the introducing of trifluoroethanol reaction back owing to the C-F chain, its water repellency further improves.
Beneficial effect
(1) water repellent finishing agent of the present invention can not produce significantly influence to gas permeability, whiteness and the ultimate strength of cellulose fibre;
(2) the more conventional Organic fluoride of water repellent finishing agent of the present invention and organosilicon water repellent finishing agent synthesis technique is simple, cost is low, the raw material environmental protection, environmental pollution is little.
Description of drawings
The chemical structure of general formula of Fig. 1 vegetable oil modified fluoride-containing water repellent finishing agent.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) add 35ml80 ℃ of hot water and 3.5g NaOH in the 20g castor oil, use the 15ml hot water dissolving, 80 ℃ of water-bath heating are stirred, and leave standstill.Add an amount of sodium chloride, the mixture of natrium ricinoleicum, sodium palmitate, odium stearate, enuatrol, linoleic acid sodium, linolenic acid sodium is separated out, glycerine is removed with sodium-chloride water solution.
(2) the mixture water-soluble of the natrium ricinoleicum that step (1) is prepared, sodium palmitate, odium stearate, enuatrol, linoleic acid sodium, linolenic acid sodium, add an amount of sulfuric acid acidation, pour standing demix in the separatory funnel into, the upper strata is ricinoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic mixture.
(3) ricinoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, the linolenic mixture 15.4g with step (2) preparation joins the CF that contains 14g
3CH
2In the OH three-necked bottle, be warming up to 60 ℃, insulation reaction 4h obtains the mixture of ricinoleic acid trifluoro ethyl ester, palmitic acid trifluoro ethyl ester, stearic acid trifluoro ethyl ester, oleic acid trifluoro ethyl ester, linoleic acid trifluoro ethyl ester, linolenic acid trifluoro ethyl ester.
The mixture of the ricinoleic acid trifluoro ethyl ester of gained, palmitic acid trifluoro ethyl ester, stearic acid trifluoro ethyl ester, oleic acid trifluoro ethyl ester, linoleic acid trifluoro ethyl ester, linolenic acid trifluoro ethyl ester is dissolved in the ether, be made into the solution of variable concentrations, be organized on the cellulose fibre, finishing technique on cellulose fibre is: finishing agent concentration 40g/L, two soak two rolls, pick-up rate 80%～90%, 100 ℃ of preliminary drying 40min, be warming up to 170 ℃, bake 3min.Arrangement finishes, and the whiteness of fabric is measured according to GB/T 8424.2-2001 " textile color stability is tested the objective ranking method of relative whiteness "; The ultimate strength of fabric is measured (wherein learn from else's experience and average for 3 times to sample testing) according to GB/T3923.1-1997 " textile fabric tensile property part 1: the assay method of ultimate strength and elongation at break "; Contact angle is measured by the JY-82 contact angle instrument; The water droplet extinction time is measured by water droplet disappearance method.The result shows that cellulose fibre has obtained excellent water repellency through after the castor oil modified trifluoro ethyl ester arrangement, and whiteness and ultimate strength have decline slightly.
Embodiment 2
Described palmitic synthetic method and the finishing technique on cellulose fibre are substantially the same manner as Example 1.The arrangement result shows that cellulose fibre has obtained excellent water repellency through after the arrangement of palm oil modification trifluoro ethyl ester, and whiteness and ultimate strength have decline slightly.
Claims (5)
1. vegetable oil modified fluoride-containing water repellent finishing agent, chemical structure of general formula is as follows:
R represents the fatty carbon chain of different carbon atoms, n=0,1,2 ... 7, this water repellent finishing agent is by different aliphatic acid and CF in the vegetable oil
3-(CF
2) n-CH
2The mixture that the ester that the OH reaction generates is formed, its proterties is light yellow to brown yellow transparent liquid.
2. a kind of vegetable oil modified fluoride-containing water repellent finishing agent according to claim 1 is characterized in that: vegetable oil modified fluoride-containing water repellent finishing agent is the mixture that following several ester is formed:
C
6H
13CHOHCH
2CH＝CH(CH
2)
7COOCH
2(CF
2)n-CF
3，
CH
3(CH
2)
7CH＝CH(CH
2)
7COOCH
2(CF
2)n-CF
3，
CH
3(CH
2)
4CH＝CH-CH
2-CH＝CH(CH
2)
7COOCH
2(CF
2)n-CF
3，
CH
3(CH
2)
14COOCH
2(CF
2) n-CF
3, CH
3(CH
2)
16COOCH
2(CF
2) n-CF
3, and
CH
3CH
2(CH＝CHCH
2)
3(CH
2)
6COOCH
2(CF
2)n-CF
3。
3. the preparation method of a kind of vegetable oil modified fluoride-containing water repellent finishing agent according to claim 1 comprises:
(1) add 70 ℃ of-100 ℃ of water and NaOH in vegetable oil, 80 ℃ of water-bath heating promptly get sodium soap;
(2) with above-mentioned sodium soap water-soluble, add sulfuric acid acidation, promptly get higher fatty acids;
(3) with above-mentioned higher fatty acids and CF
3-(CF
2) n-CH
2OH obtains vegetable oil modified fluoride-containing water repellent finishing agent at 60 ℃ of reaction 4-8h.
4. the preparation method of a kind of vegetable oil modified fluoride-containing water repellent finishing agent according to claim 3, it is characterized in that: described step (1) vegetable oil is palm oil, castor oil, peanut oil, rapeseed oil, soybean oil or cottonseed oil.
5. a kind of vegetable oil modified fluoride-containing water repellent finishing agent according to claim 1 is applied to the water repellent finish of cellulose fibre.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100547794A CN101608402B (en) | 2009-07-14 | 2009-07-14 | Vegetable oil modified fluoride-containing water repellent finishing agent as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100547794A CN101608402B (en) | 2009-07-14 | 2009-07-14 | Vegetable oil modified fluoride-containing water repellent finishing agent as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101608402A CN101608402A (en) | 2009-12-23 |
| CN101608402B true CN101608402B (en) | 2011-07-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100547794A Expired - Fee Related CN101608402B (en) | 2009-07-14 | 2009-07-14 | Vegetable oil modified fluoride-containing water repellent finishing agent as well as preparation method and application thereof |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383306B (en) * | 2011-08-10 | 2014-01-08 | 东华大学 | Fluorine-containing modified vegetable oil polymer water-repellent finishing agent, and preparation and application thereof |
| US9962357B2 (en) * | 2013-10-18 | 2018-05-08 | West Virginia University | Halogenated esters of cyclopropanated unsaturated fatty acids for use in the treatment of neurodegenerative diseases |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1509360A (en) * | 2001-05-21 | 2004-06-30 | 3M | Polymers containing perfluorovingl ethers and use thereof |
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2009
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1509360A (en) * | 2001-05-21 | 2004-06-30 | 3M | Polymers containing perfluorovingl ethers and use thereof |
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