CN101792507B - Leather waterproof fatliquoring agent - Google Patents
Leather waterproof fatliquoring agent Download PDFInfo
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- CN101792507B CN101792507B CN2010101192640A CN201010119264A CN101792507B CN 101792507 B CN101792507 B CN 101792507B CN 2010101192640 A CN2010101192640 A CN 2010101192640A CN 201010119264 A CN201010119264 A CN 201010119264A CN 101792507 B CN101792507 B CN 101792507B
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- fatty alcohol
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- fluoro
- chain aliphatic
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Abstract
The invention discloses a leather waterproof fatliquoring agent which is fluorine-containing maleic acid ester acrylic copolymer leather waterproof fatliquoring agent which is formed by the aqueous emulsion combined polymerization of long-chain fatty alcohol maleic acid monoester, fluoro-fatty alcohol maleic acid monoester and crylic acid. The leather waterproof fatliquoring agent synthetized by the invention is a high polymer material with an amphipathic structure, has favorable surfactivity, is used for processing leather and can ensure excellent washing fastness and waterproofness of leather. Organic solvent is not used in the preparation technology, which conforms to cleaning production requirements.
Description
Technical field
The invention belongs to the leather chemical industry technical field, particularly relate to a kind of fluorine-containing maleic acid ester acrylic copolymer leather water-proof fatting agent and preparation method thereof.
Background technology
Oiling is one important procedure in the process hides process, gives leather with softness and folding quality.Fatting agent has material impact at the distribution form and the consumption of leather fiber inside to performance of leather.The interaction of hydrophilic radical in the fatting agent and polar group and leather fiber has determined persistence and the validity of fatting agent in leather fiber.If fatting agent can be combined in the leather fiber surface securely, then can give leather with water-wash resistance and dry cleaning resistance energy.In addition, high-grade leather as clothing leather, had both required it to have wash durability, also required it that certain water resistance or performance of watertightness are arranged simultaneously, and therefore, leather fat should possess amphiphilic nature, and both oleophylic was hydrophilic again.The amphiphilic structure polymkeric substance is normally with lipophilicity monomer such as chain alkyl acrylate, long chain alkyl methacrylate, long chain aliphatic alcohol maleic acid ester, long-chain olefin etc. and the monomer that contains hydrophilic radical, as vinylformic acid, methacrylic acid, maleic anhydride etc., carry out the polymkeric substance that copolymerization obtains having on the molecule oil loving chain alkyl and hydrophilic radical.This polymkeric substance is because molecular weight is bigger, contain more polar group simultaneously, strong with the leather fiber binding ability, be used for the leather processing and can give the wash durability and the dry cleaning resistance energy of leather excellence, this amphiphilic structure compound can also give leather certain water resistance simultaneously.
Leather fat also should have the surface of good activity, could be evenly, firmly, stably attached on the leather, play waterproof effect, but, existing leather fat surfactivity is lower, and attachment state is not good enough on leather, and water resistance is not fully used.
Chinese patent CN101186951A discloses a kind of polymaleic anhydride aliphatic alcohol monoesters leather ester-adding agent, maleic anhydride is polymerized to oligopolymer earlier, on polymaleic anhydride, introduce Fatty Alcohol(C12-C14 and C12-C18) then, generate monoesters, and then obtain polymaleic anhydride aliphatic alcohol monoesters sodium salt with the neutralization of its sodium oxide, this fatting agent is the tensio-active agent with Gemini type structure, and is active fine.But its shortcoming is to be solvent with toluene, does not meet the requirement that cleans production.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect that prior art exists, provide a kind of and can give leather water-wash resistance and water-repellancy, has the surface of good activity simultaneously, thereby can further strengthen the leather water-proof fatting agent of amphiphilic structure polymkeric substance water resistance, technical thought is: fluorine cpd have extremely low surface energy, if introduce fluorochemicals then can further strengthen the water resistance of amphiphilic structure polymkeric substance on the amphiphilic structure polymer molecule.But the fluorochemical monomer poorly water-soluble can only carry out solution polymerization (or carrying out aqueous emulsion polymerization under the effect of solubility promoter) usually in organic solvent, do not meet the requirement that cleans production.Therefore, key problem in technology of the present invention is to seek an operational path of introducing fluorochemicals without organic solvent on the amphiphilic structure polymer molecule.
Technical scheme of the present invention is:
A kind of leather water-proof fatting agent carries out the acrylic acid multipolymer of fluorine-containing maleic acid ester that the water miscible liquid copolymerization obtains by long chain aliphatic alcohol toxilic acid monoesters, fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters and vinylformic acid, prepares as follows and gets:
(1). with long chain aliphatic alcohol, fluoro Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride, under the effect of catalyzer, carry out the mixture of single-esterification synthetic fatty alcohol toxilic acid monoesters, fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters;
(2). Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters, fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters mixture and vinylformic acid that step (1) is made carry out free radical copolymerization under action of evocating, the synthetic acrylic acid multipolymer of fluorine-containing maleic acid ester.
Described long chain aliphatic alcohol is the long chain aliphatic alcohol of C12～C18, and described fluoro Fatty Alcohol(C12-C14 and C12-C18) is C6～C8 perfluoro Fatty Alcohol(C12-C14 and C12-C18); The mass ratio of described long chain aliphatic alcohol and fluoro Fatty Alcohol(C12-C14 and C12-C18) is 70～90: 10～30, described catalyzer is an anhydrous sodium acetate, catalyst consumption is 0.5%～1.5% (based on the massfraction of reactant), the mass ratio of described long chain aliphatic alcohol, fluoro fatty alcohol mixture and maleic anhydride is 100: 34～53, temperature of reaction is 70 ℃～110 ℃, and the reaction times is 2h～5h.
Described Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters, fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters mixture and acrylic acid mass ratio are 100: 24～72, described initiator is a persulphate, the consumption of initiator is 4%～8% (based on the massfraction of reactant), temperature of reaction is 70 ℃～90 ℃, and polymerization time is 1.5h～3h.
Described cross sulfosalt be in ammonium persulphate, Sodium Persulfate, the Potassium Persulphate any.
This leather water-proof fatting agent obtains fluorine-containing maleic acid ester acrylic copolymer for carrying out the water miscible liquid copolymerization by long chain aliphatic alcohol toxilic acid monoesters, fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters and vinylformic acid.
Long chain aliphatic alcohol that long chain aliphatic alcohol toxilic acid monoesters of the present invention is C12～C18 and maleic anhydride carry out single-esterification and obtain, and the schematic reaction formula of mono-esterification is as shown in the formula shown in (1):
Formula (1) long chain aliphatic alcohol and maleic anhydride single-esterification formula (n is 12～18 integer)
By formula (1) as can be known, obtained having certain hydrophilic lipophilicity monomer behind the pure and mild maleic anhydride single-esterification of long-chain fat, can carry out aqueous emulsion polymerization with vinylformic acid.
Perfluoro Fatty Alcohol(C12-C14 and C12-C18) that fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters of the present invention is C6～C8 and maleic anhydride carry out single-esterification and obtain, and the schematic reaction formula of mono-esterification is as shown in the formula shown in (2):
Formula (2) perfluoro Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride single-esterification formula (m is 6～8 integer)
By formula (2) as can be known, obtained having certain hydrophilic fluorochemical monomer behind perfluoro Fatty Alcohol(C12-C14 and C12-C18) and the maleic anhydride single-esterification, can under the condition of organic solvent-free, carry out aqueous emulsion polymerization, more met the requirement that cleans production with vinylformic acid.
The invention has the advantages that:
Introduce fluorine component by aqueous emulsion polymerization in amphiphilic polymer, strengthened the water resistance of amphiphilic polymer, not with an organic solvent, production technique more meets environmental protection requirement in the preparation process.Fluorine-containing maleic acid ester acrylic copolymer leather water-proof fatting agent of the present invention is used for leather processing, can gives and handle leather excellent wash durability and water resistance.
Embodiment
Below in conjunction with embodiment the present invention is done further introduction, those skilled in the art can do a little nonessential adjustment according to the foregoing invention content.
Embodiment 1
With 70 parts of lauryl alcohols, 30 parts of perfluoro hexanols, 48 parts of maleic anhydrides and 0.74 part of sodium acetate, add and take back stream, in the reactor of condensation and temperature regulating device, be warming up to 85 ℃, insulation reaction 3h, be cooled to 70 ℃ then, add 159 parts of 60 ℃～70 ℃ hot water, drip 65.56 parts of mass concentrations again and be 30% aqueous sodium hydroxide solution, transfer about reactant pH value to 7.0, be warming up to 80 ℃ then, slowly drip 36.5 parts of initiator sodium persulfate aqueous solutions (6.5 parts of persulfuric acid are dissolved in 30 parts of water) simultaneously, 35.4 part vinylformic acid and 65.56 parts of mass concentrations are that (the dropping time is controlled at about 2h for 30% aqueous sodium hydroxide solution, control pH value of reaction system simultaneously about 7.0), finish, add 10 parts of sodium persulfate aqueous solutions (1.8 parts of Sodium Persulfates are dissolved in 8.2 parts of water), be warming up to 85 ℃, continue insulation reaction 1.5h, the 50 ℃ of dischargings of lowering the temperature promptly get the fluorine-containing maleic acid ester acrylic copolymer leather water-proof fatting agent of moisture content 60%.
Embodiment 2
With 70 parts of lauryl alcohols, 30 parts of perfluoro hexanols, 48 parts of maleic anhydrides and 0.74 part of sodium acetate, add and take back stream, in the reactor of condensation and temperature regulating device, be warming up to 85 ℃, insulation reaction 3h, be cooled to 70 ℃ then, add 167 parts of 60 ℃～70 ℃ hot water, drip 65.56 parts of mass concentrations again and be 30% aqueous sodium hydroxide solution, transfer about reactant pH value to 7.0, be warming up to 80 ℃ then, slowly drip 36.5 parts of initiator sodium persulfate aqueous solutions (8.0 parts of persulfuric acid are dissolved in 30 parts of water) simultaneously, 53.6 part vinylformic acid and 98.34 parts of mass concentrations are that (the dropping time is controlled at about 2h for 30% aqueous sodium hydroxide solution, control pH value of reaction system simultaneously about 7.0), finish, add 10 parts of sodium persulfate aqueous solutions (2 parts of Sodium Persulfates are dissolved in 8.2 parts of water), be warming up to 85 ℃, continue insulation reaction 1.5h, the 50 ℃ of dischargings of lowering the temperature promptly get the fluorine-containing maleic acid ester acrylic copolymer leather water-proof fatting agent of water content 60%.
Embodiment 3
With 90 parts of lauryl alcohols, 10 parts of perfluoro hexanols, 53 parts of maleic anhydrides and 1.0 parts of sodium acetates, add and take back stream, in the reactor of condensation and temperature regulating device, be warming up to 85 ℃, insulation reaction 3h, be cooled to 70 ℃ then, add 144 parts of 60 ℃～70 ℃ hot water, drip 72 parts of mass concentrations again and be 30% aqueous sodium hydroxide solution, transfer about reactant pH value to 7.0, be warming up to 80 ℃ then, slowly drip 36.5 parts of initiator sodium persulfate aqueous solutions (10 parts of persulfuric acid are dissolved in 30 parts of water) simultaneously, 53.6 part vinylformic acid and 98.34 parts of mass concentrations are that (the dropping time is controlled at about 2h for 30% aqueous sodium hydroxide solution, control pH value of reaction system simultaneously about 7.0), finish, add 10 parts of sodium persulfate aqueous solutions (2 parts of Sodium Persulfates are dissolved in 8.2 parts of water), be warming up to 85 ℃, continue insulation reaction 1.5h, the 50 ℃ of dischargings of lowering the temperature promptly get the fluorine-containing maleic acid ester acrylic copolymer leather water-proof fatting agent of water content 60%.
Sodium Persulfate in the foregoing description also can be an ammonium persulphate, or Potassium Persulphate.
Claims (2)
1. leather water-proof fatting agent, it is characterized in that, this leather water-proof fatting agent is to carry out the acrylic acid multipolymer of fluorine-containing maleic acid ester that the water miscible liquid copolymerization obtains by long chain aliphatic alcohol toxilic acid monoesters, fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters and vinylformic acid, prepares as follows and gets:
(1). with long chain aliphatic alcohol, fluoro Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride, under the effect of catalyzer, carry out the mixture of single-esterification synthetic fatty alcohol toxilic acid monoesters, fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters;
(2). Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters, fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters mixture and vinylformic acid that step (1) is made carry out free radical copolymerization under action of evocating, the synthetic acrylic acid multipolymer of fluorine-containing maleic acid ester;
Described long chain aliphatic alcohol is the long chain aliphatic alcohol of C12～C18, and described fluoro Fatty Alcohol(C12-C14 and C12-C18) is C6～C8 perfluoro Fatty Alcohol(C12-C14 and C12-C18); The mass ratio of described long chain aliphatic alcohol and fluoro Fatty Alcohol(C12-C14 and C12-C18) is 70～90: 10～30, described catalyzer is an anhydrous sodium acetate, catalyst consumption is 0.5%～1.5% massfraction based on reactant, the mass ratio of described long chain aliphatic alcohol, fluoro fatty alcohol mixture and maleic anhydride is 100: 34～53, temperature of reaction is 70 ℃～110 ℃, and the reaction times is 2h～5h; Described Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters, fluoro Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters mixture and acrylic acid mass ratio are 100: 24～72, described initiator is a persulphate, the consumption of initiator is 4%～8% massfraction based on reactant, temperature of reaction is 70 ℃～90 ℃, and polymerization time is 1.5h～3h.
2. leather water-proof fatting agent according to claim 1 is characterized in that, described persulphate be in ammonium persulphate, Sodium Persulfate, the Potassium Persulphate any.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101192640A CN101792507B (en) | 2010-03-06 | 2010-03-06 | Leather waterproof fatliquoring agent |
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| CN2010101192640A CN101792507B (en) | 2010-03-06 | 2010-03-06 | Leather waterproof fatliquoring agent |
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| Publication Number | Publication Date |
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| CN101792507A CN101792507A (en) | 2010-08-04 |
| CN101792507B true CN101792507B (en) | 2011-09-21 |
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| CN2010101192640A Expired - Fee Related CN101792507B (en) | 2010-03-06 | 2010-03-06 | Leather waterproof fatliquoring agent |
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| CN106755633A (en) * | 2016-11-15 | 2017-05-31 | 王鲁燕 | A kind of novel amphipathic copolymer composite tan fatting agent and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133372A (en) * | 1996-06-28 | 2000-10-17 | Stockhausen Gmbh & Co. Kg | Aqueous polymer dispersion, process for preparing the same and its use in leather production |
| CN101186951A (en) * | 2007-11-16 | 2008-05-28 | 陕西科技大学 | Method for preparing polymaleic anhydride aliphatic alcohol monoesters leather ester-adding agent |
| CN101279798A (en) * | 2008-05-29 | 2008-10-08 | 河北省能源研究所 | Scale-inhibiting dispersant for industry recirculated cooling water process and preparation thereof |
-
2010
- 2010-03-06 CN CN2010101192640A patent/CN101792507B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133372A (en) * | 1996-06-28 | 2000-10-17 | Stockhausen Gmbh & Co. Kg | Aqueous polymer dispersion, process for preparing the same and its use in leather production |
| CN101186951A (en) * | 2007-11-16 | 2008-05-28 | 陕西科技大学 | Method for preparing polymaleic anhydride aliphatic alcohol monoesters leather ester-adding agent |
| CN101279798A (en) * | 2008-05-29 | 2008-10-08 | 河北省能源研究所 | Scale-inhibiting dispersant for industry recirculated cooling water process and preparation thereof |
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Address after: 618000 xieyue village, Tianyuan Town, Jingyang District, Deyang City, Sichuan Province Patentee after: Sichuan desai'er New Material Technology Co.,Ltd. Address before: 618000 xieyue village, Tianyuan Town, Jingyang District, Deyang City, Sichuan Province Patentee before: DECISION CHEMICAL Co.,Ltd. |
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