CN103255243A - Preparation method of soft acrylic resin leather retanning agent - Google Patents
Preparation method of soft acrylic resin leather retanning agent Download PDFInfo
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- CN103255243A CN103255243A CN201310131242XA CN201310131242A CN103255243A CN 103255243 A CN103255243 A CN 103255243A CN 201310131242X A CN201310131242X A CN 201310131242XA CN 201310131242 A CN201310131242 A CN 201310131242A CN 103255243 A CN103255243 A CN 103255243A
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Abstract
The invention discloses a soft acrylic resin leather retanning agent and a preparation method thereof. The preparation method comprises the following steps of: firstly performing an esterification reaction based on methyl ricinoleate and maleic anhydride to generate maleic monoester of methyl ricinoleate, and neutralizing with sodium hydroxide to obtain a methyl ricinoleate maleic monoester sodium salt monomer; and then performing free radical polymerization of the methyl ricinoleate maleic monoester sodium salt monomer with a vinyl monomer in a waterborne system to obtain an acrylic resin retanning agent of which the side chain contains the methyl ricinoleate-structure long-chain lipophilic group. The retanning agent disclosed by the invention can be used for filling and retanning crust leather and also can be used for perfectly softening crust leather fiber, is a fat-liquoring type acrylic resin leather retanning agent, and realizes a certain waterproof effect on the chrome tanning crust leather.
Description
Technical field
The invention belongs to the synthetic field of leather chemicals, be specifically related to a kind of preparation method of soft type acrylic resin leather composite tanning agent.
Background technology
In leather industry, chrome tanning agent in numerous tanning agents still in occupation of dominant position.Acrylic resin retanning agent is a kind of common used material for chrome tanned leather (wet blue leather) retanning processing.Contain a large amount of carboxyls in this resinoid molecular structure, can the chromic salts coordination in chrome tanned leather be combined, have very strong selection fillibility, can improve the intensity of crust leather, the position that reduces crust leather is poor, thereby improves the utilization ratio of leather.
Yet the acrylic resin retanning agent of one-component causes crust leather stiff easily, makes crust leather fiber embrittlement, and the finished leather wear resistance descends, and produces the effect of losing colour etc.This mainly is because substituting group polarity is strong on the formed homopolymer molecular chain of principal monomer of preparation acrylic resin retanning agent, and it is intensive to arrange, and causes the multipolymer kindliness poor.Therefore, numerous investigators begin idea and manage in acrylic resin to introduce and have group or the component of soft function.
Zheng Shunji carries out esterification with Viscotrol C and maleic anhydride, generates product (Viscotrol C toxilic acid monoesters) and obtains having the multipolymer macromole composite tan fatting agent of amphiphilic structure with the Acrylic Acid Monomer copolymerization, and be applied to the leather retanning operation.Though this lubricating retanning agent has stuffing function preferably, owing to being raw material with the bigger Viscotrol C of molecule, connecting more triglyceride residue side chain on the main polymer chain, cause the penetrating quality of this retanning agent relatively poor.
Wang Jiatu etc. deliver patent CN 1397650A, use Viscotrol C and thanomin generation transesterification reaction in the embodiment, product and maleic anhydride carry out esterification and make terminal double bond containing grease monomer, at last itself and vinylformic acid are carried out free radicals copolymerization reaction and obtain greasing-retanning agnt of leather.Compare with the research of Zheng Shunji, the perviousness of retanning agent is improved largely.But reactions steps is more in its preparation method, and energy consumption is bigger.
The ricinolic acid methyl esters, its chemical name is the ricinoleic acid methyl esters, is mainly used in the synthetic of special organic compound.Present stage, comparatively rare with the domestic relevant report of ricinolic acid methyl esters feedstock production greasing-retanning agnt of leather.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the present invention aims to provide a kind of soft type acrylic resin leather composite tanning agent and preparation method thereof.This retanning agent can also soft crust leather fiber except possessing the retanning function, give the chrome tanning crust leather certain water-repellancy, and its preparation method is simple, and energy consumption is less.
In order to achieve the above object, the present invention takes following technical scheme:
A kind of soft type acrylic resin leather composite tanning agent is to make with ricinolic acid methyl esters toxilic acid monoester sodium salt monomer and vinyl monomer free radicals copolymerization reaction, and its structural representation is as follows:
Wherein:
M, n, k, h all represent the number of repeat unit of corresponding monomer,
m=1～100，n=1～100，k=1～20，h=1～75。
The preparation method of this soft type acrylic resin leather composite tanning agent may further comprise the steps:
1), vinyl monomer is mixed with monomer solution; The dilute with water ammonium persulphate is made into initiator solution;
2), react with ricinolic acid methyl esters and maleic anhydride, make ricinolic acid methyl esters toxilic acid monoesters;
3), in the ricinolic acid methyl esters toxilic acid monoesters dropping sodium aqueous solution, the reaction back adds deionized water, the back of heating up drips monomer solution and the initiator solution that makes in the step 1) synchronously, question response is complete, namely gets this retanning agent product.
Described vinyl monomer is vinylformic acid sodium salt, sodium salt of methacrylic acid, acrylamide.
Described monomer solution comprises monomer solution A and B, and wherein, the compound method of monomer solution A is, with vinylformic acid, methacrylic acid and aqueous sodium hydroxide solution reaction; The compound method of monomer solution B is to mix with ionized water with acrylamide, chain regulator.
Described various monomer mass ratio is respectively, ricinolic acid methyl esters toxilic acid monoester sodium salt 10%～30%, vinylformic acid sodium salt and sodium salt of methacrylic acid total amount 40%～70%, acrylamide 10%～30%.
Described chain regulator is Virahol, 1, and one of 2-propylene glycol, its consumption are 5%～10% of whole monomer total masses.
The consumption of described initiator solution is 2.0%～6.0% conversion of whole monomer total masses by the ammonium persulphate quality.
The present invention has the following advantages:
1, is uniform-distribution with the long linear alkylene side chain of comparatively unfolding on the main chain of polymer retanning agent disclosed by the invention, uses it for chrome-tanned retanning, can softly remove from office fiber, give crust leather certain water-repellancy, and its penetrating quality is better.
2, the present invention is raw material with the ricinolic acid methyl esters, prepares resin retaning agent by the esterification of ricinolic acid methyl esters and maleic anhydride and the copolyreaction of product and water-soluble ethylene base class monomer thereof.Compare with similar retanning agent, preparation method of the present invention can save transesterify (or alcoholysis) reaction of Viscotrol C, has simplified the production route, has reduced production cost.
Embodiment
Specifically describe below by the present invention of embodiment, only be used for the present invention is further specified, can not be interpreted as limiting the scope of the invention.
Embodiment one
1) 15.0 gram vinylformic acid, 17.9 gram methacrylic acids are added in the there-necked flask, at 20～30 ℃ of aqueous sodium hydroxide solutions that slowly add 55.6 gram mass concentration 30% down, reacted 30 minutes, obtain monomer solution A1; 12.0 gram acrylamides, 3.0 gram Virahols and 40 gram deionized waters are mixed, obtain monomer solution B1; Be made into the initiator solution C1 of mass concentration 5% with 3.6 gram ammonium persulphates; Standby.
2) in the there-necked flask that agitator and reflux condensing tube are housed, add 31.2 gram ricinolic acid methyl esters and 10.3 gram maleic anhydrides, be warming up to 90 ℃, reacted 4 hours, obtain ricinolic acid methyl esters toxilic acid monoesters;
3) add 4.3 gram ricinolic acid methyl esters toxilic acid monoesters in the four-hole boiling flask that agitator is housed, stir, drip behind the aqueous sodium hydroxide solution of 1.8 gram mass concentration 30% in 20～30 ℃ of reactions 30 minutes.Add 23.7 gram deionized waters, be warming up to 75～80 ℃, in 2.5～3.0 hours, drip monomer solution A1, monomer solution B1 and initiator solution C1 in the step 1) simultaneously, the three dropwises the back simultaneously and continues reaction 1 hour down at 80～82 ℃, namely gets milk yellow thick liquid retanning agent 1.
Embodiment two
1) 15.0 gram vinylformic acid, 17.9 gram methacrylic acids are added in the there-necked flask, at 20～30 ℃ of aqueous sodium hydroxide solutions that slowly add 55.6 gram mass concentration 30% down, reacted 30 minutes, obtain monomer solution A2; 6.0 gram acrylamides, 6.0 gram 1,2-propylene glycol and 40 gram deionized waters are mixed, obtain monomer solution B2; Be made into the initiator solution C2 of mass concentration 5% with 2.4 gram ammonium persulphates; Standby;
2) in the there-necked flask that agitator and reflux condensing tube are housed, add 31.2 gram ricinolic acid methyl esters and 10.3 gram maleic anhydrides, be warming up to 110 ℃, reacted 2.5 hours, obtain ricinolic acid methyl esters toxilic acid monoesters;
3) add 8.7 gram ricinolic acid methyl esters toxilic acid monoesters in the four-hole boiling flask that agitator is housed, stir, drip behind the aqueous sodium hydroxide solution of 3.7 gram mass concentration 30% in 20～30 ℃ of reactions 30 minutes.Add 44.7 gram deionized waters, be warming up to 75～80 ℃, in 2.5～3.0 hours, drip step 2 simultaneously) in monomer solution A2, monomer solution B2 and initiator solution C2, the three dropwises the back simultaneously and continues reaction 1 hour down at 80～82 ℃, namely gets milk yellow thick liquid retanning agent 2.
Embodiment three
1) 8.6 gram vinylformic acid, 10.2 gram methacrylic acids are added in the there-necked flask, at 20～30 ℃ of aqueous sodium hydroxide solutions that slowly add 31.9 gram mass concentration 30% down, reacted 30 minutes, obtain monomer solution A3; 18.0 gram acrylamides, 3.0 gram Virahols and 40 gram deionized waters are mixed, obtain monomer solution B3; Be made into the initiator solution C3 of mass concentration 5% with 1.2 gram ammonium persulphates; Standby;
2) in the there-necked flask that agitator and reflux condensing tube are housed, add 31.2 gram ricinolic acid methyl esters and 10.3 gram maleic anhydrides, be warming up to 120 ℃, reacted 2 hours, obtain ricinolic acid methyl esters toxilic acid monoesters;
3) in the four-hole boiling flask that agitator is housed, add 13.0 gram ricinolic acid methyl esters toxilic acid monoesters, stir, reacted 30 minutes in 20～30 ℃ behind the aqueous sodium hydroxide solution of Dropwise 5 .5 gram mass concentration 30%.Add 86.0 gram deionized waters, be warming up to 75～80 ℃, in 2.5～3.0 hours, drip step 2 simultaneously) in monomer solution A3, monomer solution B3 and initiator solution C3, the three dropwises the back simultaneously and continues reaction 1 hour down at 80～82 ℃, namely gets milk yellow thick liquid retanning agent 3.
The retanning application experiment
The goat upper wet blue leather experimentizes after getting a shaving.To being split into four, label is 1#, 2#, 3#, 4# along back line and center line.1# is the control group laboratory sample, is the acrylic resin retanning agent DESOTAN SV that Sichuan DeSaiEr chemical engineering Industry Co.,Ltd produces, and its excess-three group uses retanning agent 1, retanning agent 2 and retanning agent 3 in the embodiment of the invention as resin retaning agent respectively.Implementing process is as shown in table 1:
Table 1 soft type acrylic resin leather composite tanning agent application experiment
Flexibility to four compacts leather after the perviousness of four kinds of retanning agents and the retanning stuffing thereof is carried out sensory evaluation, the perviousness of retanning agent 1～10 minute, the flexibility of crust leather 1～10 minute.The result is as shown in table 2:
Table 2 retanning agent effect
As can be seen from Table 2, three kinds of retanning agents of experimental group can give crust leather certain flexibility, and along with the increase (being that the proportion of ricinolic acid methyl esters toxilic acid monoester sodium salt in total monomer increases) of long linear alkylene side chain number on the retanning agent resin chain, the flexibility of crust leather strengthens.On the other hand, the perviousness of these three kinds of retanning agents is compared more inferior slightly with acrylate copolymer DESOTAN SV.But all in all, retanning agent disclosed by the invention has excellent application performance.
Claims (7)
1. a soft type acrylic resin leather composite tanning agent is to make with ricinolic acid methyl esters toxilic acid monoester sodium salt monomer and vinyl monomer free radicals copolymerization reaction, and its structural representation is as follows:
Wherein:
M, n, k, h all represent the number of repeat unit of corresponding monomer,
m=1～100，n=1～100，k=1～20，h=1～75。
2. the preparation method of the described soft type acrylic resin of claim 1 leather composite tanning agent may further comprise the steps:
1), vinyl monomer is mixed with monomer solution; The dilute with water ammonium persulphate is made into initiator solution;
2), react with ricinolic acid methyl esters and maleic anhydride, make ricinolic acid methyl esters toxilic acid monoesters;
3), in the ricinolic acid methyl esters toxilic acid monoesters dropping sodium aqueous solution, the reaction back adds deionized water, the back of heating up drips monomer solution and the initiator solution that makes in the step 1) synchronously, question response is complete, namely gets this retanning agent product.
3. the preparation method of soft type acrylic resin leather composite tanning agent according to claim 2, it is characterized in that: described vinyl monomer is vinylformic acid sodium salt, sodium salt of methacrylic acid, acrylamide.
4. the preparation method of soft type acrylic resin leather composite tanning agent according to claim 2, it is characterized in that: described monomer solution comprises monomer solution A and B, wherein, the compound method of monomer solution A is, with vinylformic acid, methacrylic acid and aqueous sodium hydroxide solution reaction; The compound method of monomer solution B is to mix with ionized water with acrylamide, chain regulator.
5. the preparation method of soft type acrylic resin leather composite tanning agent according to claim 4, it is characterized in that: described various monomer mass ratios are respectively, ricinolic acid methyl esters toxilic acid monoester sodium salt 10%～30%, vinylformic acid sodium salt and sodium salt of methacrylic acid total amount 40%～70%, acrylamide 10%～30%.
6. the preparation method of soft type acrylic resin leather composite tanning agent according to claim 4, it is characterized in that: described chain regulator is Virahol, 1, one of 2-propylene glycol, its consumption are 5%～10% of whole monomer total masses.
7. the preparation method of soft type acrylic resin leather composite tanning agent according to claim 4 is characterized in that: the consumption of described initiator solution is 2.0%～6.0% conversion of whole monomer total masses by the ammonium persulphate quality.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107586896A (en) * | 2017-09-30 | 2018-01-16 | 浙江盛汇化工有限公司 | A kind of thermal stimulus response type acrylic hydrogel leather composite tanning agent and preparation method |
| CN109321693A (en) * | 2018-10-10 | 2019-02-12 | 许昌鑫瑞德化工科技有限公司 | A kind of preparation method of leather acrylic acid double tanning agent |
| CN110862496A (en) * | 2019-11-12 | 2020-03-06 | 安徽旭升新材料有限公司 | Castor oil polymer and preparation method thereof |
| CN110938169A (en) * | 2019-11-21 | 2020-03-31 | 安徽旭升新材料有限公司 | Preparation method of castor oil ester-acrylamide-acrylic acid copolymer |
| CN111454423A (en) * | 2020-04-29 | 2020-07-28 | 东莞市冠力胶业有限公司 | Water-based vacuum plastic and preparation method thereof |
| CN111777738A (en) * | 2020-07-28 | 2020-10-16 | 陕西科技大学 | Vegetable oil derivative modified amphoteric polyurethane retanning agent and preparation method thereof |
| CN112921133A (en) * | 2021-02-26 | 2021-06-08 | 郑州科信化工有限公司 | Resin retanning agent |
| CN113817883A (en) * | 2021-10-15 | 2021-12-21 | 四川亭江新材料股份有限公司 | Sulfonate-containing polymer retanning fatliquor and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107586896A (en) * | 2017-09-30 | 2018-01-16 | 浙江盛汇化工有限公司 | A kind of thermal stimulus response type acrylic hydrogel leather composite tanning agent and preparation method |
| CN109321693A (en) * | 2018-10-10 | 2019-02-12 | 许昌鑫瑞德化工科技有限公司 | A kind of preparation method of leather acrylic acid double tanning agent |
| CN110862496A (en) * | 2019-11-12 | 2020-03-06 | 安徽旭升新材料有限公司 | Castor oil polymer and preparation method thereof |
| CN110938169A (en) * | 2019-11-21 | 2020-03-31 | 安徽旭升新材料有限公司 | Preparation method of castor oil ester-acrylamide-acrylic acid copolymer |
| CN111454423A (en) * | 2020-04-29 | 2020-07-28 | 东莞市冠力胶业有限公司 | Water-based vacuum plastic and preparation method thereof |
| CN111777738A (en) * | 2020-07-28 | 2020-10-16 | 陕西科技大学 | Vegetable oil derivative modified amphoteric polyurethane retanning agent and preparation method thereof |
| CN111777738B (en) * | 2020-07-28 | 2021-10-15 | 陕西科技大学 | Vegetable oil derivative modified amphoteric polyurethane retanning agent and preparation method thereof |
| CN112921133A (en) * | 2021-02-26 | 2021-06-08 | 郑州科信化工有限公司 | Resin retanning agent |
| CN113817883A (en) * | 2021-10-15 | 2021-12-21 | 四川亭江新材料股份有限公司 | Sulfonate-containing polymer retanning fatliquor and preparation method thereof |
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| CN103255243B (en) | 2015-01-21 |
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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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