CN115304563B - Maleic acid ester modifier, polymerized acrylic resin derivative, and preparation methods and applications thereof - Google Patents
Maleic acid ester modifier, polymerized acrylic resin derivative, and preparation methods and applications thereof Download PDFInfo
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
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- 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
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- C14C3/22—Chemical tanning by organic agents using polymerisation products
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Abstract
The invention provides a maleic acid ester modifier, a polymeric acrylic resin derivative, and a preparation method and application thereof, and relates to the technical field of polymers. The modifier provided by the invention comprises a maleimide modifier (preparation raw materials: maleic anhydride and diethanolamine) and/or a maleic acid ester modifier (preparation raw materials: maleic anhydride and sorbitol anhydride ester compounds). The polymer acrylic resin derivative provided by the invention has a plurality of active functional groups including hydroxyl, carboxyl and double bonds, and the branching degree and the crosslinking degree of the polymer acrylic resin derivative prepared by using the modifier are improved, and the polymer acrylic resin derivative is applied to leather, so that the moisture retention of the leather can be improved.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to a maleic acid ester modifier, a polymeric acrylic resin derivative, a preparation method and application thereof.
Background
In the leather industry, the polymerized acrylic resin is an important synthetic tanning agent, contains more carboxyl in the molecule, can be bonded with amino groups of leather collagen or complexed with chromium ions of chrome leather to form multi-point crosslinking, has a certain tanning property, is commonly used in a retanning procedure of leather processing, has good filling property, and the leather treated by the polymerized acrylic resin has good light fastness and compactibility and improves mechanical property. However, the conventional polymerized acrylic resin has many disadvantages for leather, such as hard leather, poor rebound resilience of leather, rough grain surface of leather, easy embrittlement of leather, poor folding endurance, poor rewet, certain color failure effect on the coloring of anionic dye, and low dyeing vividness.
The water content of the common leather embryo is about 14-18 wt%, and in the storage process, the leather often becomes dry and hard due to the change of environmental conditions such as air temperature, improper storage and the like, the quality of the leather is affected, and the leather is usually required to be added with rewetting oil (such as emulsified rapeseed oil, beef tallow, polyethylene glycol oleate and the like) for rewetting, so that the fiber is restored to moisten and loosen. However, the moisturizing effect of the conventional rewet oil is not good enough.
Disclosure of Invention
In view of the above, the invention aims to provide a maleic acid ester modifier, a polymeric acrylic resin derivative, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a maleic acid ester modifier, which is obtained by esterification reaction of maleic anhydride and sorbitan ester compounds;
the esterification reaction product comprises at least one of compounds with structures shown in formula I and formula II:
in the formula I, R 1 comprises-OOC-CH=CH-COOH, -OH or-OOCR, - (OCH) 2 CH 2 ) a OOCR；R 2 comprising-OOC-CH=CH-COOH, -OH or- (OCH) 2 CH 2 ) b OOCR；R 3 comprising-C (OH) CH 2 OOCR、-C(OOC-CH＝CH-COOH)CH 2 OOCR or-C (- (OCH) 2 CH 2 ) c OOCR)(OCH 2 CH 2 ) d OOC-CH＝CH-COOH；
In the formula II, R 4 comprises-O (OCH) 2 CH 2 ) c OOC、-O(OCH 2 CH 2 ) c OC-ch=ch-COOH or-CH 3 ；R 5 comprises-O (OCH) 2 CH 2 ) b H or-O (OCH) 2 CH 2 ) b OC-CH＝CH-COOH；R 6 comprises-O (OCH) 2 CH 2 ) a OC-ch=ch-COOH or-O (OCH) 2 CH 2 ) a H；
Wherein R independently comprises a stearic acid group, a oleic acid group, a lauric acid group or a palmitic acid group, and a to d independently are integers.
Preferably, the sorbitan ester compound comprises one or more of sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) sorbitan monooleate and polyoxyethylene (20) sorbitan trioleate.
Preferably, the molar ratio of the maleic anhydride to the sorbitan ester compound is 1: (0.5-3).
Preferably, the temperature of the esterification reaction is 80-150 ℃ and the time is 3-5 h.
The invention provides a polymerized acrylic resin derivative, which comprises the following preparation raw materials in parts by mass: 20-200 parts of acrylic acid, 0-2400 parts of modifier which is not 0 part, 0.1-20 parts of initiator and 80-10880 parts of water;
the modifier comprises a maleamide modifier and/or a maleate modifier, wherein the maleate modifier is the maleate modifier in the technical scheme;
the maleic amide modifier comprises an acylation product and/or a hyperbranched esterification product of maleic anhydride and diethanolamine.
Preferably, the preparation method of the maleamides modifier comprises the following steps of;
maleic anhydride and diethanolamine are mixed for acylation reaction to obtain an acylated product;
and mixing the acylated product with an acid catalyst, and performing self-esterification reaction to obtain a hyperbranched esterified product.
Preferably, the acidic catalyst comprises one or more of p-toluenesulfonic acid, concentrated sulfuric acid and solid acid;
the solid acid comprises one or more of immobilized liquid acid, acid oxide, transition metal sulfide, phosphate, sulfate, zeolite molecular sieve, heteropolyacid, cation exchange resin, natural clay mineral and solid super acid.
Preferably, the mass ratio of the maleic amide modifier to the maleic ester modifier in the modifier is (0-400): (0-2000).
The invention provides a preparation method of the polymerized acrylic resin derivative, which comprises the following steps:
mixing a maleic amide modifier and/or a maleic ester modifier with water, an initiator and acrylic acid, and carrying out polymerization reaction to obtain the polymerized acrylic resin derivative.
The invention also provides an application of the polymerized acrylic resin derivative prepared by the technical scheme or the preparation method of the technical scheme as a leather auxiliary agent.
The invention provides a maleic acid ester modifier which is obtained by esterification reaction of maleic anhydride and sorbitan ester compounds. The maleic acid ester modifier provided by the invention contains a plurality of hydroxyl groups, can form hydrogen bond crosslinking with water to lock water, and also contains oleic acid groups to have good moisturizing effect on fibers, so that the moisturizing performance of leather can be improved. In addition, the maleic acid ester modifier provided by the invention has a plurality of active functional groups such as carboxyl, hydroxyl and double bonds, and the active functional groups in the modifier and vinyl of acrylic acid are subjected to copolymerization reaction in the process of preparing the polymerized acrylic acid resin derivative by using the maleic acid ester modifier as the modifier, so that the branching degree and crosslinking degree of the polymerized acrylic acid resin derivative can be improved.
The invention provides a preparation method of the polymerized acrylic resin derivative. The preparation method provided by the invention is simple to operate, low in cost and low in production cost, and the preparation raw materials are easy to obtain, so that the preparation method is suitable for industrial production.
The invention provides a polymerized acrylic resin derivative, which comprises the following preparation raw materials in parts by mass: 20-200 parts of acrylic acid, 0-2400 parts of modifier which is not 0 part, 0.1-20 parts of initiator and 80-10880 parts of water; the modifier comprises a maleamide modifier and/or a maleate modifier, wherein the maleate modifier is the maleate modifier in the technical scheme; the maleic amide modifier comprises an acylation product and/or a hyperbranched esterification product of maleic anhydride and diethanolamine. Traditional aqueous polymerized acrylic resin (such as LEATAN R12) is polymerized by acrylic acid, and has no moisturizing effect after use. The polymeric acrylic resin derivative provided by the invention contains a plurality of hydroxyl groups and oleic acid groups, and can remarkably improve the moisture retention performance of leather. The acrylic resin film formed on the leather surface by the traditional water-based polymerized acrylic resin (such as LEATAN R12) has strong brittleness, so that the leather has poor tearing resistance, a leather board is hard, the grain surface is thicker, the rebound resilience of the leather after embossing is poor, and the pressure-resistant effect is poor. In the polymerized acrylic resin derivative provided by the invention, the polymerized acrylic resin derivative is provided with a plurality of active functional groups, the polymerized acrylic resin derivative, acrylic acid and a crosslinking agent react and polymerize, so that the branching degree and crosslinking degree of acrylic resin can be improved remarkably, a polymerized acrylic resin derivative film with high flexibility can be formed on the surface of leather by the polymerized acrylic resin derivative, the tear resistance, the pressure resistance and the rebound resilience of leather can be improved remarkably, and the comprehensive mechanical property of leather is improved. Moreover, the leather has better moisturizing effect and moisture retention on fibers, and has small leather astringency effect and fine grain surface. In addition, the polymeric acrylic resin derivative provided by the invention uses water as a solvent, does not generate three wastes, and is environment-friendly. The moisture retention rate of the leather treated by the polymeric acrylic resin derivative provided by the invention is more than 58.22%, and the moisture retention performance of the leather can be obviously improved.
The invention provides a preparation method of the polymerized acrylic resin derivative. The preparation method provided by the invention is simple to operate, low in cost and low in production cost, and the preparation raw materials are easy to obtain, so that the preparation method is suitable for industrial production.
Detailed Description
The invention provides a maleic acid ester modifier, which is obtained by esterification reaction of maleic anhydride and sorbitan ester compounds;
the esterification reaction product comprises at least one of compounds with structures shown in formula I and formula II:
in the formula I, R 1 comprises-OOC-CH=CH-COOH, -OH or-OOCR, - (OCH) 2 CH 2 ) a OOCR；R 2 comprising-OOC-CH=CH-COOH, -OH or- (OCH) 2 CH 2 ) b OOCR；R 3 comprising-C (OH) CH 2 OOCR、-C(OOC-CH＝CH-COOH)CH 2 OOCR or-C (- (OCH) 2 CH 2 ) c OOCR)(OCH 2 CH 2 ) d OOC-CH＝CH-COOH；
In the formula II, R 4 comprises-O (OCH) 2 CH 2 ) c OOC、-O(OCH 2 CH 2 ) c OC-ch=ch-COOH or-CH 3 ；R 5 comprises-O (OCH) 2 CH 2 ) b H or-O (OCH) 2 CH 2 ) b OC-CH＝CH-COOH；R 6 comprises-O (OCH) 2 CH 2 ) a OC-ch=ch-COOH or-O (OCH) 2 CH 2 ) a H；
Wherein R independently comprises a stearic acid group, a oleic acid group, a lauric acid group or a palmitic acid group, and a to d independently are integers.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
In the present invention, the compound having the structure shown in formula I preferably includes at least one of the structures shown in formulas I-1 to I-9, as shown in Table 1:
TABLE 1 Compounds of the structures shown in formulas I-1 to I-9
In the present invention, R in the formulae I-8 to I-9 shown independently preferably includes a stearic group or an oleic group, and the sum of a, b, c and d (i.e., the addition number of ethylene oxide) in the formula I-9 is preferably 20.
In the present invention, the compound of the structure shown in formula II preferably includes at least one of the structures shown in formulas II-1 to II-7, as shown in Table 2:
TABLE 2 Compounds of the structures shown in formulas II-1 to II-7
In the present invention, the sum of a, b and c (i.e., the addition number of ethylene oxide) in formulas II-1 to II-5 and formula II-7 is independently preferably 20, and the sum of a and b in formula II-6 is preferably 20.
In the present invention, the sorbitan ester compounds preferably include one or more of sorbitan monolaurate (span 20), sorbitan monopalmitate (span 40), sorbitan monostearate (span 60), sorbitan tristearate (span 65), sorbitan monooleate (span 80), sorbitan trioleate (span 85), polyoxyethylene (20) sorbitan monolaurate (tween 20), polyoxyethylene (20) sorbitan monopalmitate (tween 40), polyoxyethylene (20) sorbitan monostearate (tween 60), polyoxyethylene (20) sorbitan tristearate (tween 65), polyoxyethylene (20) sorbitan monooleate (tween 80) and polyoxyethylene (20) sorbitan trioleate (tween 85). In the present invention, the molar ratio of the sorbitan ester compound to maleic anhydride is preferably 1: (0.5 to 3), more preferably 1: (0.8 to 2.5), more preferably 1: (0.9-2).
In the present invention, the preparation method of the maleate-type modifier preferably comprises the following steps: mixing maleic anhydride and a sorbitol anhydride ester compound, and carrying out esterification reaction to obtain the maleic anhydride modifier. The mixing mode is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing; the temperature of the mixing is preferably 50 to 80 ℃, more preferably 60 to 70 ℃, and the time of the mixing is not particularly limited in the present invention, and the mixing may be carried out until the maleic anhydride is completely melted. In the present invention, the order of mixing is preferably to add maleic anhydride 1 to 15 times to the sorbitan ester compound for mixing. In the present invention, the temperature of the esterification reaction (denoted as the third esterification reaction) is preferably 80 to 150 ℃, more preferably 90 to 150 ℃; the time of the esterification reaction is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours. After the completion of the esterification reaction, the present invention preferably further comprises cooling the resulting esterification reaction system to 30 to 40 ℃ (more preferably 32 to 38 ℃, still more preferably 35 to 36 ℃), and the cooling means is not particularly limited, and may be any cooling means known to those skilled in the art, and specifically, such as natural cooling.
The invention provides a polymerized acrylic resin derivative, which comprises the following preparation raw materials in parts by mass: 20-200 parts of acrylic acid, 0-2400 parts of modifier which is not 0 part, 0.1-20 parts of initiator and 80-10880 parts of water;
the modifier comprises a maleamide modifier and/or a maleate modifier, wherein the maleate modifier is the maleate modifier in the technical scheme;
the maleic amide modifier comprises an acylation product and/or a hyperbranched esterification product of maleic anhydride and diethanolamine.
The preparation raw materials of the polymerized acrylic resin derivative provided by the invention comprise 20-200 parts of acrylic acid, preferably 30-200 parts, and more preferably 50-200 parts by mass.
The preparation raw materials of the polymerized acrylic resin derivative provided by the invention comprise 0-2400 parts by mass of modifier, preferably 200-2200 parts by mass, more preferably 300-2000 parts by mass and still more preferably 500-1500 parts by mass of modifier, wherein the modifier comprises maleic amide modifier and/or maleic ester modifier, and the maleic ester modifier is the maleic ester modifier in the technical scheme. In the invention, the mass ratio of the maleic amide modifier to the maleic ester modifier in the modifier is preferably (0-400): (0 to 2000), more preferably (0 to 200): (200 to 2000), more preferably (0 to 50): (300-2000).
In the present invention, the preparation method of the maleamide-based modifier preferably comprises the steps of: maleic anhydride and diethanolamine are mixed for acylation reaction to obtain an acylated product; and mixing the acylated product with an acid catalyst, and performing self-esterification reaction to obtain a hyperbranched esterified product.
The invention mixes maleic anhydride and diethanolamine to carry out acylation reaction to obtain the acylation product (namely, the acylation product of maleic anhydride and diethanolamine). In the present invention, the molar ratio of diethanolamine to maleic anhydride is preferably 1: (0.8 to 1.2), more preferably 1: (0.9 to 1.1), more preferably 1: (1-1.02). The mixing mode is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing; the temperature of the mixing is preferably less than or equal to 45 ℃, more preferably 20-40 ℃; the mixing time is preferably 3 to 10 hours, more preferably 5 to 8 hours. In the invention, the mixing sequence is preferably that maleic anhydride is added into diethanolamine for 5-20 times for mixing; after each maleic anhydride addition, the mixture was mixed until the maleic anhydride was completely melted, and then maleic anhydride was added again. In the present invention, the temperature of the acylation reaction is preferably 20 to 40 ℃, more preferably 25 to 35 ℃; the time for the acylation reaction is preferably 0.5 to 5 hours, more preferably 1 to 4 hours, and still more preferably 2 to 3 hours. In the present invention, the structural formula of the acylation product is preferably shown in the formula III-1:
after the acylated product is obtained, the acylated product is mixed with an acid catalyst, and self-esterification reaction is carried out to obtain a hyperbranched esterified product (namely, hyperbranched esterified product of maleic anhydride and diethanolamine). In the present invention, the acidic catalyst preferably includes one or more of p-toluenesulfonic acid, concentrated sulfuric acid and solid acid. In the present invention, the concentration of the concentrated sulfuric acid is preferably 98% by weight or more. In the present invention, the solid acid preferably includes one or more of immobilized liquid acid, acidic oxide, transition metal sulfide, phosphate, sulfate, zeolite molecular sieve, heteropolyacid, cation exchange resin, natural clay mineral and solid super acid. In the present invention, the immobilized liquid acid preferably comprises HF/Al 2 O 3 、BF 3 /Al 2 O 3 And H 3 PO 4 One or more of/diatomite. In the present invention, the acidic oxide preferably includes Al 2 O 3 、SiO 2 、B 2 O 3 、Nb 2 O 5 、Al 2 O 3 -SiO 2 And Al 2 O 3 -B 2 O 3 One or more of them. In the present invention, the transition metal is vulcanizedThe material preferably comprises one or both of CdS and ZnS. In the present invention, the phosphate preferably comprises AlPO 4 And BPO 4 One or two of them. In the present invention, the sulfate preferably includes Fe 2 (SO 4 ) 3 、Al 2 (SO 4 ) 3 And CuSO 4 One or more of them. In the present invention, the zeolite molecular sieve preferably includes one or more of ZSM-5 zeolite, X zeolite, Y zeolite, B zeolite, mordenite and AIRO SAPO molecular sieve. In the present invention, the heteropoly acid preferably includes H 3 PW 12 O 40 、H 4 SiW 12 O 40 And H 3 PMo 12 O 40 One or more of them. In the present invention, the cation exchange resin preferably includes one or both of styrene-divinylbenzene copolymer and Nafion-H. In the present invention, the natural clay mineral preferably includes one or more of kaolin, bentonite and montmorillonite. In the present invention, the solid superacid preferably comprises SO 4 2- /ZrO 2 、WO 3 /ZrO 2 、MoO 3 /ZrO 2 And B 2 O 3 /ZrO 2 One or more of them. In the present invention, the mass of the acidic catalyst is 0.1 to 2%, more preferably 0.5 to 1.5%, still more preferably 1% of the total mass of maleic anhydride and diethanolamine. The mixing mode is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing; the temperature of the mixing is preferably 50 to 90 ℃, more preferably 60 to 70 ℃. In the present invention, the esterification reaction preferably includes sequentially performing a first esterification reaction and a second esterification reaction; the temperature of the first esterification reaction is preferably 100-150 ℃, more preferably 120-130 ℃, and the time of the first esterification reaction is preferably 1-6 h, more preferably 2h; the temperature of the second esterification reaction is preferably 120 to 180 ℃, more preferably 150 to 160 ℃, and the time of the second esterification reaction is preferably 0.5 to 3 hours, more preferably 1 to 2 hours. In the invention, in the esterification reaction process, an acylation product is subjected to esterification reaction under the action of an acid catalyst to form a hyperbranched esterified polymer. Completion houseAfter the esterification reaction, the present invention preferably further comprises cooling the obtained esterification reaction system to 100℃or lower (more preferably 20 to 40 ℃), and the cooling method is not particularly limited, and a cooling method known to those skilled in the art, specifically, natural cooling may be employed.
In the present invention, the structural formula of the hyperbranched esterification product is preferably shown as formula III-2:
wherein, the liquid crystal display device comprises a liquid crystal display device,representing repeating structural units.
The preparation raw materials of the polymerized acrylic resin derivative provided by the invention comprise 0.1-20 parts of initiator, preferably 0.2-10 parts, more preferably 0.2-5 parts, and even more preferably 0.2-2.5 parts by mass of acrylic acid. In the present invention, the initiator preferably includes one or more of persulfate, peroxide, azo-based compound, and peroxide-reducing agent mixture; the persulfate preferably comprises one or more of potassium persulfate, sodium persulfate and ammonium persulfate; the azo compound preferably comprises one or more of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate and azodiisobutylamidine hydrochloride; the peroxide in the peroxide and peroxide-reducing agent mixture independently preferably includes one or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, alkyl peroxide (di-t-butyl peroxide, dicumyl peroxide, t-butyl benzoate peroxide, t-butyl t-amyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl oxide, dicyclohexyl peroxydicarbonate and hydrogen peroxide, the reducing agent in the peroxide-reducing agent mixture preferably includes one or more of ferrous sulfate, cuprous sulfate, sodium bisulfite, sodium metabisulfite, sodium dithionite and glucose, and the molar ratio of peroxide to reducing agent in the peroxide-reducing agent mixture is preferably 1 (0.5-2), more preferably 1 (1-1.5). In the present invention, the initiator is preferably used in the form of an aqueous initiator solution, the concentration of which is preferably 10-50 wt%, more preferably 20-25 wt%.
The raw materials for preparing the polymeric acrylic resin derivative provided by the invention comprise, by mass, 80-10880 parts of water, preferably 500-10000 parts, more preferably 700-8000 parts, and even more preferably 850-6500 parts. In the present invention, the water is preferably distilled water and/or deionized water.
The raw materials for preparing the polymerized acrylic resin derivative provided by the invention preferably further comprise 5-100 parts, preferably 10-80 parts, more preferably 12-50 parts, and even more preferably 14-40 parts of a pH regulator, based on the mass parts of the acrylic acid. In the present invention, the pH adjustor preferably includes an inorganic base and/or an organic base, and the inorganic base preferably includes one or more of sodium hydroxide, potassium hydroxide, and aqueous ammonia; the organic base preferably comprises one or more of ethanolamine, diethanolamine, triethanolamine and 2-amino-2-methyl-1-propanol; the concentration of the aqueous ammonia is preferably 10 to 25wt%, more preferably 15 to 20wt%.
In the present invention, the mass fraction of the polymerized acrylic resin derivative is preferably 15 to 35wt%, more preferably 25 to 31wt%.
The invention provides a preparation method of the polymerized acrylic resin derivative, which comprises the following steps: mixing a maleic amide modifier and/or a maleic ester modifier with water, an initiator and acrylic acid, and carrying out polymerization reaction to obtain the polymerized acrylic resin derivative.
In a specific embodiment of the present invention, the method for preparing the polymerized acrylic resin derivative preferably comprises the steps of:
mixing a modifying agent with a part of pH regulator to obtain a modified mixed solution; the pH value of the modified mixed solution is 3-6;
mixing the modified mixed solution with part of water, an initiator and acrylic acid, and carrying out polymerization reaction to obtain a polymerization reaction solution;
and mixing the polymerization reaction liquid with the rest of pH regulator and the rest of water to obtain the polymerized acrylic resin derivative.
The invention mixes the modifier with partial pH regulator to obtain modified mixed solution; the pH value of the modified mixed solution is 3-6. The invention is not particularly limited in the proportion of the partial pH adjuster to the total mass of the pH adjuster, and the pH of the modified mixed solution obtained may be adjusted to 3 to 6, and the pH is more preferably 4 to 5.5. The mixing mode is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing; the temperature of the mixing is preferably 30 to 70 ℃, more preferably 50 to 70 ℃. In a specific embodiment of the invention, the mixing is preferably: after heating the modifier to 30-70 ℃, adding part of the pH regulator to adjust the pH value to 3-6, and then continuing mixing for 30-60 min (more preferably 40-50 min). In the invention, the pH value of the modified mixed solution is more preferably 4-5.5, the polymerization activities are different under different pH values, the pH value is too low, the reaction speed is slower, and the invention can improve the reaction speed and improve the preparation efficiency of the polymerized acrylic resin derivative by controlling the pH value of the modified mixed solution in the range.
After the modified mixed solution is obtained, the modified mixed solution is mixed with part of water, an initiator and acrylic acid to carry out polymerization reaction, so as to obtain a polymerization reaction solution. In the present invention, the mass of the partial water is preferably 25 to 70% of the total mass of water, more preferably 32 to 62%. The mode of the mixing is not particularly limited in the present invention, and the raw materials may be uniformly mixed, and in particular, the raw materials may be mixed by stirring. In a specific embodiment of the invention, the mixing is preferably: mixing the modified mixed solution with part of water for 30-60 min (more preferably 40-50 min), heating to 80-90 ℃ (more preferably 82-90 ℃), dropwise adding an initiator aqueous solution for 5-30 min (more preferably 10 min), then dropwise adding acrylic acid at the same time, and continuously dropwise adding the initiator aqueous solution for 5-30 min (more preferably 10 min) after the acrylic acid is completely dropwise added; the dropping time of the acrylic acid is preferably 2 to 4 hours, more preferably 2.5 to 4 hours. In the present invention, the temperature of the polymerization reaction is preferably 80 to 90 ℃, more preferably 82 to 90 ℃; the polymerization time is preferably 1 to 10 hours, more preferably 2 to 5 hours.
After the polymerization reaction liquid is obtained, the polymerization reaction liquid, the rest pH regulator and the rest water are mixed to obtain the polymerized acrylic resin derivative. The mode of the mixing is not particularly limited in the present invention, and the raw materials may be uniformly mixed, and in particular, the raw materials may be mixed by stirring. In a specific embodiment of the invention, the mixing is preferably: the temperature of the polymerization reaction liquid is reduced to 40 to 50 ℃ (more preferably 45 ℃), the remaining pH adjustor is added dropwise to a pH value of 5 to 7 (more preferably 5 to 6.5), and then the remaining distilled water is added for mixing.
The invention also provides an application of the polymerized acrylic resin derivative prepared by the technical scheme or the preparation method of the technical scheme as a leather auxiliary agent. In the present invention, the polymeric acrylic resin derivative is preferably used alone as a leather retanning agent or in combination with other leather retanning agents.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Adding diethanolamine into reaction equipment, slowly adding maleic anhydride for 8 times, controlling the temperature to be lower than 45 ℃ by ice bath, continuously adding maleic anhydride after the maleic anhydride is completely melted in the diethanolamine, continuously acylating for 2 hours after the maleic anhydride is added for 5 hours to obtain an acylated product (N, N-dihydroxyethyl maleamic acid, shown in formula III-1), heating to 70 ℃, adding p-toluenesulfonic acid, continuously heating to 120 ℃ for 2 hours, heating to 150 ℃ for 1 hour, cooling to be lower than 100 ℃, and adding distilled water to adjust the solid content to 50wt percent to obtain a hyperbranched esterified product (shown in formula III-2). Wherein the molar ratio of diethanolamine to maleic anhydride=1:1, and the mass of p-toluenesulfonic acid is 1% of the total mass of diethanolamine and maleic anhydride.
Example 2
Adding Tween 80 into reaction equipment, heating to 60 ℃, adding maleic anhydride for 12 times, stirring until the maleic anhydride is melted, continuously heating to 90 ℃ and then reacting for 3 hours, and cooling to 40 ℃ to obtain a maleic acid ester modifier (a mixture of products with structures shown in formulas II-4 to II-7); wherein, the mol ratio of Tween 80 to maleic anhydride is 1:1.5.
Example 3
Adding Tween 85 into reaction equipment, heating to 60 ℃, adding maleic anhydride for 10 times, stirring until maleic anhydride is melted, continuously heating to 150 ℃, reacting for 5 hours, and cooling to 30 ℃ to obtain a maleate modifier (the product is shown as a formula I-9, wherein a+b+c+d=20); wherein, the mol ratio of Tween 85 to maleic anhydride is 1:0.9.
Example 4
Adding span 40 into reaction equipment, heating to 60 ℃, adding maleic anhydride for 5 times, stirring until the maleic anhydride is melted, continuously heating to 120 ℃ and then reacting for 4 hours, and cooling to 40 ℃ to obtain a maleic acid ester modifier (a product is a mixture with a structure shown as a formula I-4 to I-7); wherein, the mole ratio of span 40 to maleic anhydride is 1:2.
Example 5
20g of the maleic amide modifier prepared in example 1 (hyperbranched esterification product) and 300g of the maleic acid ester modifier prepared in example 2 are added into a reaction device, the temperature is raised to 50 ℃, 6g of monoethanolamine is added to adjust the pH value to 4.1, stirring is carried out for 30min, 400g of distilled water is added, stirring is continued for 60min, then heating is carried out to 82 ℃, 20wt% of azodiisobutylamidine hydrochloride solution (total mass of the initiator aqueous solution) is added dropwise, 50g of acrylic acid is simultaneously started to be added dropwise after 10min, 3h of acrylic acid is completely added dropwise, then the initiator aqueous solution is continuously added dropwise, then the reaction is carried out for 3h at 85 ℃, the temperature is reduced to 45 ℃, 8g of monoethanolamine is added dropwise, the pH value of the system is adjusted to 6.2, 460g of distilled water is slowly added to adjust the solid content to 31wt%, and the polymerized acrylic resin derivative (brown viscous liquid) is obtained.
Example 6
2000g of the maleic acid ester modifier prepared in example 3 is added into a reaction device, the temperature is raised to 70 ℃, 30g of sodium hydroxide is added to adjust the pH value to 5.3, stirring is carried out for 60min, 2000g of distilled water is added, stirring is continued for 60min, then heating is carried out to 90 ℃, 20g of acrylic acid is simultaneously added dropwise after 25wt% of sodium persulfate aqueous solution (the total mass of the initiator aqueous solution is 10 g) is added dropwise for 10min, 2h of acrylic acid is completely added dropwise, then the initiator aqueous solution is continuously added dropwise for 10min, then the reaction is carried out for 3h at 90 ℃, the temperature is reduced to 50 ℃, 5g of sodium hydroxide is added to adjust the pH value of the system to 5.7, 4165g of distilled water is slowly added to adjust the solid content to 25.3wt% to obtain the polymerized acrylic resin derivative (brown viscous liquid).
Example 7
500g of the maleic acid ester modifier prepared in example 4 is added into a reaction device, the temperature is raised to 70 ℃, 20g of ammonia water with the concentration of 17wt% is added to adjust the pH value to 4.7, the mixture is stirred for 60min, 1000g of distilled water is added and then the mixture is continuously stirred for 30min, then the mixture is heated to 80 ℃, 200g of acrylic acid is simultaneously added dropwise after 10min of ammonium persulfate aqueous solution with the concentration of 25wt% (the total mass of the initiator aqueous solution is 3 g), the initiator aqueous solution is continuously added dropwise after 4h of acrylic acid is completely added dropwise, the mixture is reacted for 10min, the mixture is reacted for 3h at 88 ℃, the temperature is reduced to 48 ℃,10 g of ammonia water with the concentration of 17wt% is added to adjust the pH value of the system to 6.1, 630g of distilled water is slowly added to adjust the solid content to 31wt%, and the polymerized acrylic resin derivative (brown viscous liquid) is obtained.
Comparative example 1
Waterborne polymeric acrylic resin LEATAN R12 (Qihe Lichun chemical Co., ltd.).
Application example 1
Taking 4 pieces of the same part of the blue wet leather of the cow leather, adding 0.2% degreasing agent FB (Qihe Lichu chemical Co., ltd.) and 0.5% oxalic acid, transferring at 40deg.C for 2h, draining, adding 100% water, adding 4% chromiumTanning with powder retanning for 6h, draining, adding 1.2% sodium bicarbonate and 1% sodium formate for neutralization, performing retanning, adding 15% retanning agent (the retanning agent is the polymerized acrylic resin derivative prepared in examples 5-7, the water-based polymerized acrylic resin LEATAN R12 prepared in comparative example 1) respectively, treating in a drum at 35deg.C for 1.5h, draining, adding the same amount of universal fatliquor BUXOM SS (manufactured by Qiher chemical Co., ltd.), treating in a drum at 50deg.C for 1h, adding formic acid with blue wet skin mass of 1.2% for fixation, wherein formic acid is diluted with water with three times the formic acid mass, each time for 10min, washing with water, taking out, vacuum drying at 70deg.C under 100kPa for 10min, testing the moisturizing property of the treated leather, airing the treated leather at room temperature to constant weight, and weighing (m) Tare weight ) Then dried to constant weight at a constant temperature of 60 ℃ and weighed (denoted as m) Dry tare weight ) Moisture retention = m Dry tare weight /m Tare weight 100% and the results are shown in Table 3. The mass percentages are calculated by a blue wet cortex meter.
Table 3 effects of application of the leather assistants provided in examples 5 to 7 and comparative example 1
| Retanning agent | Tare/g | Dry weight/g | Moisture retention percentage% | Softness and softness | Grain fineness |
| Example 5 | 718.3 | 449.9 | 62.64 | 2.573 | Careful and careful |
| Example 6 | 740.6 | 473.5 | 63.93 | 2.514 | Careful and careful |
| Example 7 | 663.5 | 386.3 | 58.22 | 2.455 | Careful and careful |
| Comparative example 1 | 691.9 | 361.3 | 52.22 | 2.064 | Finer and finer |
As can be seen from table 1, the moisture retention rate of the leather treated with the polymeric acrylic resin derivative provided by the invention is above 58.22%, and the polymeric acrylic resin derivative provided by the invention can significantly improve the moisture retention performance of the leather.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A maleic acid ester modifier is characterized in that the maleic acid ester modifier is obtained by esterification reaction of maleic anhydride and a sorbitol anhydride ester compound; the sorbitan ester compound is sorbitan monopalmitate, polyoxyethylene (20) sorbitan trioleate or polyoxyethylene (20) sorbitan monooleate;
the product of the esterification reaction has at least one of the compounds with the structures shown in the formulas I-4 to I-7, I-9 and II-4 to II-7:
wherein R in the formulas I-9 and II-4 to II-7 is oleic acid group, R in the formulas I-4 to I-7 is palmitic acid group; a+b+c+d=20 in formula I-9, a+b+c=20 in formulas II-4, II-5 and II-7, and a+b=20 in formula II-6.
2. The maleic anhydride modifier according to claim 1, wherein the molar ratio of maleic anhydride to sorbitan ester compound is 1: (0.5-3).
3. The maleate-type modifier according to claim 1, wherein the esterification reaction is carried out at a temperature of 80-150 ℃ for a period of 3-5 hours.
4. The polymerized acrylic resin derivative comprises the following preparation raw materials in parts by mass: 20-200 parts of acrylic acid, 0-2400 parts of modifier which is not 0 part, 0.1-20 parts of initiator and 80-10880 parts of water;
the modifier is maleic anhydride modifier or maleic amide modifier and maleate modifier, wherein the maleate modifier is the maleate modifier of any one of claims 1-3;
the maleimide modifier is an acylation product and/or hyperbranched esterification product of maleic anhydride and diethanolamine;
the mass ratio of the maleic amide modifier to the maleic acid ester modifier in the modifier is (0-400): (0-2000), and the amount of the maleate modifier is not 0.
5. The polymeric acrylic resin derivative according to claim 4, wherein the method for preparing the maleimide-based modifier comprises the steps of;
maleic anhydride and diethanolamine are mixed for acylation reaction to obtain an acylated product;
and mixing the acylated product with an acid catalyst, and performing self-esterification reaction to obtain a hyperbranched esterified product.
6. The polymerized acrylic resin derivative according to claim 5, wherein the acidic catalyst is one or more of p-toluenesulfonic acid, concentrated sulfuric acid and a solid acid;
the solid acid is one or more of immobilized liquid acid, acid oxide, transition metal sulfide, phosphate, sulfate, zeolite molecular sieve, heteropolyacid, cation exchange resin, natural clay mineral and solid super acid.
7. The method for producing a polymerized acrylic resin derivative according to any one of claims 4 to 6, comprising the steps of:
mixing a maleic amide modifier and/or a maleic ester modifier with water, an initiator and acrylic acid, and carrying out polymerization reaction to obtain the polymerized acrylic resin derivative.
8. Use of the polymerized acrylic resin derivative according to any one of claims 4 to 6 or the polymerized acrylic resin derivative prepared by the preparation method according to claim 7 as a leather aid.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381457A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院成都有机化学有限公司 | Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin |
| CN101845524A (en) * | 2010-06-09 | 2010-09-29 | 齐河力厚化工有限公司 | Method for preparing acrylic acid retanning agent by using oxidation reduction system as initiator |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381457A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院成都有机化学有限公司 | Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin |
| CN101845524A (en) * | 2010-06-09 | 2010-09-29 | 齐河力厚化工有限公司 | Method for preparing acrylic acid retanning agent by using oxidation reduction system as initiator |
Non-Patent Citations (2)
| Title |
|---|
| 超支化丙烯酸-马来酸酐皮革复鞣剂的合成与应用;刘军海;李志洲;王俊宏;;中国皮革(第11期);第47-50页，，尤其是文章摘要，第1.2节合成工艺 * |
| 超支化聚合物复鞣剂的制备及应用;王学川;袁绪政;丁建华;刘燕;;中国皮革(第23期);第40-44页，，尤其是第41页1.2节内容 * |
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