CN108220501B - Composite leather epoxy resin compound fatting agent and preparation method thereof - Google Patents
Composite leather epoxy resin compound fatting agent and preparation method thereof Download PDFInfo
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- CN108220501B CN108220501B CN201810195011.8A CN201810195011A CN108220501B CN 108220501 B CN108220501 B CN 108220501B CN 201810195011 A CN201810195011 A CN 201810195011A CN 108220501 B CN108220501 B CN 108220501B
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- leather
- epoxy resin
- aqueous solution
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- resin compound
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- 239000010985 leather Substances 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 title abstract description 20
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 18
- 125000000129 anionic group Chemical group 0.000 claims abstract description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 235000019198 oils Nutrition 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 7
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004359 castor oil Substances 0.000 claims description 7
- 235000019438 castor oil Nutrition 0.000 claims description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000006757 chemical reactions by type Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to a composite epoxy resin compound fatting agent for leather and a preparation method thereof, which are improved on the basis of an applied patent of anionic reaction type polyelectrolyte and a preparation method and application thereof (application number: 201710767652.1), so that the softness and physical and mechanical properties of the leather are obviously improved, the leather is endowed with good hand feeling and use experience, the problem that the fatting agent is easy to migrate under the conditions of high temperature and the like is improved to a certain extent, and the phenomenon of oil frost is avoided.
Description
Technical Field
The invention belongs to the technical field of preparation of fatting agents, and relates to an epoxy resin compound fatting agent for compound leather and a preparation method thereof.
Background
The tanning industry is an important component of foreign trade exports in China, and the output value reaches hundreds of billions of yuan. The high-grade leather consumer products are more and more popular with people, and correspondingly, the requirements of people on the performance of finished leather are higher and higher. The atomization value is one of important limiting conditions for the use of high-grade leather, and the use experience of the leather in industries such as automobiles and furniture is seriously influenced. The fat liquor is a chemical which occupies the largest proportion of chemical materials used in the leather making process and endows leather with certain physical and mechanical properties, service performance, excellent flexibility and other properties, so that the research of fat liquor products with different properties is a hot point invented at home and abroad. Among them, the polymer surfactant has low toxicity and excellent emulsifying property and film-forming property, so that the fatting agents with excellent performances such as amphiphilic polymer fatting agent, hyperbranched polymer fatting agent, modified grease polymer fatting agent and the like are gradually paid attention to by the broad inventors.
The main components (effective substances) of the fat-liquoring agent can be classified into two parts of neutral oil and emulsified components, the proportion and matching degree of the two main components seriously affect the emulsifying degree and the emulsifying stability of the compound fat-liquoring agent, and finally affect the softness, the hand feeling and the like of the leather after fat-liquoring. Under the normal condition, the stable storage of the greasing agent can be realized by adopting the micromolecular surfactant, the greasing effect is good, but with the rise of the temperature, the grease adsorbed in the leather fiber and the micromolecular surfactant can gradually migrate to the leather interface, so that the phenomenon of oil frost is caused, and the use experience of the leather is seriously influenced. Due to the weak migration capability and low toxicity of the polymer-based surfactant, the polymer-based fatting agent gradually receives attention, so that the migration phenomenon of the small molecular surfactant is overcome, and the content of grease in a fatting agent system can be increased due to the excellent emulsifying property and compatibilization effect of the polymer-based surfactant, so that the small molecular surfactant is prevented from being excessively used to a certain extent.
The invention is further improved on the basis that allyl glycidyl ether, acrylamide, butyl acrylate and sodium allylsulfonate are adopted as monomers in the processes of bin, liepengfei and the like, and a free radical polymerization method is adopted to prepare a polyelectrolyte with good surface activity in one step (an anionic reaction type polyelectrolyte, a preparation method and an application thereof, application number: 201710767652.1), so that the composite epoxy resin compound fatliquor with good performance for leather is prepared. Finally, the composite epoxy resin compound fatting agent for leather with good performance is prepared by screening different grease types and exploring factors such as different mass ratios, shearing rates, shearing time and the like.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a composite leather epoxy resin compound fatliquor and a preparation method thereof. The prepared polyelectrolyte contains epoxy groups, can be fixedly combined with collagen fibers, and further improves the fatliquoring effect of the epoxy resin compound fatliquor for the composite leather.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the preparation method of the epoxy resin compound fatliquor for the compound leather is characterized by comprising the following steps: 8-14 parts by weight of reactive polyelectrolyte is dissolved in 22-36 parts by weight of water, and then the mixture is respectively placed with 50-70 parts by weight of castor oil, rapeseed oil or white oil at the rotating speed of 3000 r/min of 2000-plus materials for high-speed shearing for 15-30 minutes, thus obtaining the optimal composite epoxy resin compound fatliquor for leather.
The composite epoxy resin compound fatting agent for leather is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the preparation process provided by the invention is simple, the industrialization is easy, and the product has excellent placement stability; the method is applied to a leather greasing procedure to determine an optimal preparation process. The leather is fatliquored by the epoxy resin compound fatliquor for compound leather prepared by the invention, the fatliquoring process is simple, the softness of the fatliquored leather is obviously improved, and the mechanical property is also improved.
Drawings
Figure 1 shows the softness and tensile strength of leather after fatliquoring.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The invention provides a preparation method of an epoxy resin compound fatliquor for compound leather, which is characterized by comprising the following steps: 8-14 parts by weight of reactive polyelectrolyte is dissolved in 22-36 parts by weight of water, and then the mixture is respectively placed with 50-70 parts by weight of castor oil, rapeseed oil or white oil at the rotating speed of 3000 r/min of 2000-plus materials for high-speed shearing for 15-30 minutes, thus obtaining the optimal composite epoxy resin compound fatliquor for leather.
The composite epoxy resin compound fatting agent for leather is prepared by the preparation method.
Patent "anionic reaction type polyelectrolyte and preparation method and application thereof" application number: 201710767652.1 the contents of the preparation method of the anionic reactive polyelectrolyte are as follows:
the preparation method of the anionic reactive polyelectrolyte comprises the following steps:
adding a sodium bisulfite aqueous solution into a four-neck flask, and then heating the mixture to 65-80 ℃ in a water bath;
mixing allyl glycidyl ether and butyl acrylate to prepare a monomer mixed solution;
mixing acrylamide and sodium allylsulfonate to prepare a mixed aqueous solution;
respectively and simultaneously dripping the mixed aqueous solution of acrylamide and sodium allylsulfonate, the mixed monomer solution and the aqueous solution of ammonium persulfate into a reactor for 0.5-1.5 h;
reacting for 3-5h at constant temperature, and cooling to room temperature to prepare the anionic reactive polyelectrolyte;
the mass ratio of the sodium bisulfite, the allyl glycidyl ether, the butyl acrylate, the acrylamide, the sodium allyl sulfonate in the sodium bisulfite aqueous solution and the ammonium persulfate in the ammonium persulfate aqueous solution is (0.7-0.9): (12-16): (2-4): (6-10): (3.0-3.6).
The sodium bisulfite aqueous solution is prepared by dissolving 0.7g-0.9g of sodium bisulfite in 26g-28g of distilled water.
The mixed water solution of sodium allylsulfonate and acrylamide is prepared by dissolving 6g-10g of sodium allylsulfonate and 2g-4g of acrylamide in 18-23g of distilled water.
The allyl glycidyl ether and butyl acrylate monomer solution is prepared by mixing 12g-16g of allyl glycidyl ether and 2g-4g of butyl acrylate.
The ammonium persulfate aqueous solution is prepared by dissolving 3g-3.5g of ammonium persulfate in 30g-35g of distilled water.
The anion reactive polyelectrolyte prepared by the preparation method.
The following examples are given in parts by weight,
example 1
And (3) dissolving 9 parts of reactive polyelectrolyte in 24 parts of water, and then respectively placing the solution and 68 parts of castor oil, rapeseed oil and white oil at a rotating speed of 25000 r/min, and shearing at a high speed for 20 min to obtain the composite epoxy resin compound fatliquor for leather.
Example 2
And dissolving 13 parts of reactive polyelectrolyte in 35 parts of water, and then respectively placing the solution and 55 parts of castor oil, rapeseed oil and white oil at a rotating speed of 3000 revolutions per minute, and shearing at a high speed for 30 minutes to obtain the composite epoxy resin compound fatliquor for leather.
Example 3
Dissolving 11 parts of reactive polyelectrolyte in 39 parts of water, and then respectively placing the water, 50 parts of castor oil, rapeseed oil and white oil at the rotating speed of 2300 revolutions per minute, and shearing at high speed for 19 minutes to obtain the composite epoxy resin compound fatliquor for leather.
Example 4
Dissolving 10 parts of reactive polyelectrolyte in 30 parts of water, and then respectively placing the solution and 60 parts of castor oil, rapeseed oil and white oil at the rotating speed of 2200 rpm, and shearing at high speed for 25 minutes to obtain the composite epoxy resin compound fatliquor for leather.
The preparation process provided by the invention is simple, the industrialization is easy, and the product has excellent placement stability; the method is applied to a leather greasing procedure to determine an optimal preparation process. The leather is fatliquored by the epoxy resin compound fatliquor for compound leather prepared by the invention, the fatliquoring process is simple, the softness of the fatliquored leather is obviously improved, and the mechanical property is also improved.
The intradermal fat content is greatly enhanced compared to commercially available products, as shown in particular in FIG. 1. In addition, the epoxy resin compound fat liquor for the compound leather also reaches 1.16 times of the fat content in the leather after being fatliquored of similar commercial products, so the epoxy resin compound fat liquor is particularly suitable for producing leather with light and soft requirements such as sofa leather, clothing leather and the like.
The matching degree of the components of the fatting agent in the system is adjusted by adjusting the proportion of the using amounts of different components, so that the matching degree of the epoxy group content and the action point of the collagen fiber of the leather is further adjusted. Finally, the good permeation and fixation of the composite epoxy resin composite fatting agent for leather are realized, the leather is endowed with delicate and soft hand feeling, and the excellent fatting effect is achieved.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (2)
1. The preparation method of the epoxy resin compound fatliquor for the compound leather is characterized by comprising the following steps: dissolving 8-14 parts by weight of reactive polyelectrolyte in 22-36 parts by weight of water, and then respectively placing the solution and 50-70 parts by weight of castor oil, rapeseed oil and white oil at a rotating speed of 2000-3000 r/min, and carrying out high-speed shearing for 15-30 min to obtain the epoxy resin compound fatliquor for compound leather; the preparation method of the reactive polyelectrolyte comprises the following steps: adding a sodium bisulfite aqueous solution into a four-neck flask, and then heating the mixture to 65-80 ℃ in a water bath; mixing allyl glycidyl ether and butyl acrylate to prepare a monomer mixed solution; mixing acrylamide and sodium allylsulfonate to prepare a mixed aqueous solution; respectively and simultaneously dripping the mixed aqueous solution of acrylamide and sodium allylsulfonate, the mixed monomer solution and the aqueous solution of ammonium persulfate into a reactor for 0.5-1.5 h; reacting for 3-5h at constant temperature, and cooling to room temperature to prepare the anionic reactive polyelectrolyte; the mass ratio of the sodium bisulfite, the allyl glycidyl ether, the butyl acrylate, the acrylamide, the sodium allyl sulfonate in the sodium bisulfite aqueous solution and the ammonium persulfate in the ammonium persulfate aqueous solution is (0.7-0.9): (12-16): (2-4): (6-10): (3.0-3.6).
2. The composite leather epoxy resin fat liquor prepared by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810195011.8A CN108220501B (en) | 2018-03-09 | 2018-03-09 | Composite leather epoxy resin compound fatting agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810195011.8A CN108220501B (en) | 2018-03-09 | 2018-03-09 | Composite leather epoxy resin compound fatting agent and preparation method thereof |
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| Publication Number | Publication Date |
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| CN108220501A CN108220501A (en) | 2018-06-29 |
| CN108220501B true CN108220501B (en) | 2020-07-28 |
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| CN111154030B (en) * | 2020-02-07 | 2021-04-27 | 四川大学 | Preparation and application of polyoxyalkylene-containing epoxy acrylate polymer active fatliquor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536092A (en) * | 2003-04-10 | 2004-10-13 | 上海皮革化工厂 | Composite leather super fatting agent and tis preparation method |
| CN101457263A (en) * | 2008-11-25 | 2009-06-17 | 陕西科技大学 | Amphoteric phosphate fat-liquoring agent containing silicon and preparation method thereof |
| CN101760570A (en) * | 2009-12-29 | 2010-06-30 | 温州大学 | Composite leather greasing agent and preparation method thereof |
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2018
- 2018-03-09 CN CN201810195011.8A patent/CN108220501B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536092A (en) * | 2003-04-10 | 2004-10-13 | 上海皮革化工厂 | Composite leather super fatting agent and tis preparation method |
| CN101457263A (en) * | 2008-11-25 | 2009-06-17 | 陕西科技大学 | Amphoteric phosphate fat-liquoring agent containing silicon and preparation method thereof |
| CN101760570A (en) * | 2009-12-29 | 2010-06-30 | 温州大学 | Composite leather greasing agent and preparation method thereof |
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Effective date of registration: 20210312 Address after: 712000 nanweisan Road, Yangling Demonstration Area, Xianyang City, Shaanxi Province Patentee after: Shaanxi Tongrui New Technology Co.,Ltd. Address before: 710021 Shaanxi city of Xi'an province Weiyang University City Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
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Denomination of invention: Composite fatliquoring agent of epoxy resin for leather and its preparation method Effective date of registration: 20220926 Granted publication date: 20200728 Pledgee: Yangling Nongke Financing Guarantee Co.,Ltd. Pledgor: Shaanxi Tongrui New Technology Co.,Ltd. Registration number: Y2022980016458 |
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Granted publication date: 20200728 Pledgee: Yangling Nongke Financing Guarantee Co.,Ltd. Pledgor: Shaanxi Tongrui New Technology Co.,Ltd. Registration number: Y2022980016458 |