CN115304563A - Maleic ester modifier, polymerized acrylic resin derivative, and preparation method and application thereof - Google Patents
Maleic ester modifier, polymerized acrylic resin derivative, and preparation method and application thereof Download PDFInfo
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- CN115304563A CN115304563A CN202211069100.0A CN202211069100A CN115304563A CN 115304563 A CN115304563 A CN 115304563A CN 202211069100 A CN202211069100 A CN 202211069100A CN 115304563 A CN115304563 A CN 115304563A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- 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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- C07D309/02—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
- 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
- C07D309/10—Oxygen atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
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Abstract
The invention provides a maleic ester modifier, a polymerized 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 maleic amide modifier (the preparation raw materials are maleic anhydride and diethanol amine) and/or a maleic anhydride ester modifier (the preparation raw materials are maleic anhydride and a sorbitol anhydride ester compound). The polyacrylic resin derivative provided by the invention has a plurality of active functional groups of hydroxyl, carboxyl and double bond, and the branching degree and the crosslinking degree of the polyacrylic resin derivative prepared by using the modifier can improve the moisture retention performance of leather when being applied to leather.
Description
Technical Field
The invention relates to the technical field of polymers, and particularly relates to a maleic ester modifier, a polymerized acrylic resin derivative, and a preparation method and application thereof.
Background
In leather industry, the polyacrylic resin is an important synthetic tanning agent, the molecules of the polyacrylic resin contain more carboxyl, the polyacrylic resin can be bonded with amino of leather collagen or complexed with chromium ions of chrome leather to form multi-point crosslinking, the polyacrylic resin has certain tanning property, is commonly used in a retanning procedure of leather processing, has good filling property, and the leather processed by the polyacrylic resin has good light resistance and compactness and improved mechanical property. However, the traditional polyacrylic resin has more defects for leather, such as the leather board becomes hard after use, the leather has poor resilience, the grain surface of the leather is thick, the leather is easy to become brittle, the folding resistance is poor, the moisture regain is poor, a certain color fading effect is caused on the coloring of anionic dye, and the dyeing vividness is low.
The water content of the general 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 and the like or improper storage and the like, so that the quality of the leather is affected, and usually, rewetting oil (such as emulsified rapeseed oil, neatsfoot oil, polyethylene glycol oleate and the like) needs to be added for re-treatment in a drum, so that the fiber is restored, moistened and loosened. However, the moisturizing effect of the conventional rewetting oil is not good enough.
Disclosure of Invention
In view of the above, the present invention aims to provide a maleic acid ester modifier, a polymeric acrylic resin derivative, and a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a maleic anhydride modifier, which is obtained by esterification reaction of maleic anhydride and sorbitan ester compounds;
the product of the esterification reaction comprises at least one of compounds having the structures shown in formula I and formula II:
in the formula I, R 1 including-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 including-O (OCH) 2 CH 2 ) c OOC、-O(OCH 2 CH 2 ) c OC-CH = CH-COOH or-CH 3 ；R 5 including-O (OCH) 2 CH 2 ) b H or-O (OCH) 2 CH 2 ) b OC-CH＝CH-COOH；R 6 comprising-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, an oleic acid group, a lauric acid group or a palmitic acid group, and a-d are independently integers.
Preferably, the sorbitan ester-based compound includes 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 weight: 20-200 parts of acrylic acid, 0-2400 parts but not 0 part of modifier, 0.1-20 parts of initiator and 80-10880 parts of water;
the modifier comprises a maleic amide modifier and/or a maleic ester modifier, and the maleic ester modifier is the maleic ester modifier in the technical scheme;
the maleic amide modifier comprises acylation products and/or hyperbranched esterification products of maleic anhydride and diethanol amine.
Preferably, the preparation method of the maleic amide modifier comprises the following steps;
mixing maleic anhydride and diethanol amine, and carrying out acylation reaction to obtain an acylation product;
and (3) mixing the acylation product with an acidic catalyst, and carrying out self-esterification reaction to obtain a hyperbranched esterification 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, acidic oxide, transition metal sulfide, phosphate, sulfate, zeolite molecular sieve, heteropoly acid, cation exchange resin, natural clay mineral and solid super acid.
Preferably, the mass ratio of the maleic amide modifier to the maleic diacid ester modifier in the modifier is (0-400): (0 to 2000).
The invention provides a preparation method of the polymerized acrylic resin derivative, which comprises the following steps:
and mixing the maleic amide modifier and/or the maleic acid 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 the application of the polymerized acrylic resin derivative in the technical scheme or the polymerized acrylic resin derivative prepared by the preparation method in the technical scheme as a leather assistant.
The invention provides a maleic anhydride 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 an oleic acid group to have a good moistening effect on fibers, so that the moisture retention 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, double bond and the like, in the process of preparing the polymerized acrylic resin derivative by using the maleic acid ester modifier as the modifier, the active functional groups in the modifier and vinyl of acrylic acid generate copolymerization reaction, the branching degree and the crosslinking degree of the polymerized acrylic resin derivative can be improved, the polymerized acrylic resin derivative is applied to leather as a leather retanning agent, and a polymerized acrylic resin derivative film formed on the surface of the leather has high flexibility, so that the tear resistance, the pressure resistance, the rebound resilience and the fineness of the grain surface of the leather are obviously improved.
The invention provides a preparation method of the polymerized acrylic resin derivative in the technical scheme. The preparation method provided by the invention is simple to operate, cheap and easily available in preparation raw materials, low in production cost and suitable for industrial production.
The invention provides a polymerized acrylic resin derivative which comprises the following preparation raw materials in parts by weight: 20 to 200 portions of acrylic acid, 0 to 2400 portions of modifier but not 0 portion, 0.1 to 20 portions of initiator and 80 to 10880 portions of water; the modifier comprises a maleic amide modifier and/or a maleic ester modifier, and the maleic ester modifier is the maleic ester modifier in the technical scheme; the maleic amide modifier comprises acylation products and/or hyperbranched esterification products of maleic anhydride and diethanol amine. Traditional waterborne acrylic resin (such as LEATAN R12) is polymerized by acrylic acid, and has no moisturizing effect after being used. The polymerized acrylic resin derivative provided by the invention contains a plurality of hydroxyl groups and oleic acid groups, and can obviously improve the moisture retention performance of leather. The acrylic resin film formed on the surface of leather by the traditional waterborne polymerization acrylic resin (such as LEATAN R12) has strong brittleness, so that the leather has poor tear resistance, a leather plate is hard, the grain surface is thick, the resilience of the embossed leather is poor, and the pressure-resistant effect is poor. In the polymerized acrylic resin derivative provided by the invention, the polymerized acrylic resin derivative has a plurality of active functional groups, the polymerized acrylic resin derivative, acrylic acid and a cross-linking agent react and polymerize to improve the branching degree and the cross-linking degree of the acrylic resin, and the polymerized acrylic resin derivative can form a polymerized acrylic resin derivative film with high flexibility on the surface of leather, so that the tear resistance, the pressure resistance and the resilience of the leather can be improved remarkably, and the comprehensive mechanical property of the leather is improved. Moreover, the leather has better moistening effect and moisture retention effect on fibers, small leather astringency effect and fine leather grain surface. In addition, the polymerized acrylic resin derivative provided by the invention takes water as a solvent, does not generate three wastes, and is green and environment-friendly. The moisture retention rate of the leather treated by the polyacrylic resin derivative provided by the invention is above 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 in the technical scheme. 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 cheap and easy to obtain, so that the preparation method is suitable for industrial production.
Detailed Description
The invention provides a maleic anhydride modifier, which is obtained by esterification reaction of maleic anhydride and sorbitan ester compounds;
the product of the esterification reaction comprises at least one of compounds having the structures shown in formula I and formula II:
in the formula I, R 1 including-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 Included-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 including-O (OCH) 2 CH 2 ) c OOC、-O(OCH 2 CH 2 ) c OC-CH = CH-COOH or-CH 3 ；R 5 including-O (OCH) 2 CH 2 ) b H or-O (OCH) 2 CH 2 ) b OC-CH＝CH-COOH；R 6 including-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, an oleic acid group, a lauric acid group or a palmitic acid group, and a-d are independently integers.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the compound of formula I preferably includes at least one of the structures of formulas I-1 to I-9, as shown in Table 1:
TABLE 1 Compounds of the formulae I-1 to I-9
In the present invention, R in the formulae I-8 to I-9 shown independently preferably includes a stearic acid group or an oleic acid group, and the sum of a, b and c (i.e., the addition number of ethylene oxide) in the formula I-9 is preferably 20.
In the present invention, the compound of formula II preferably includes at least one of the structures of formulae II-1 to II-7, as shown in Table 2:
TABLE 2 Compounds of the formulae II-1 to II-7
In the present invention, the sum of a, b, c and d (i.e., the adduct number of ethylene oxide) in the formula II-8 shown is preferably 20.
In the present invention, the sorbitan ester-based compound preferably includes 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-based 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 modifier preferably comprises the following steps: and mixing maleic anhydride and a sorbitan ester compound, and carrying out esterification reaction to obtain the maleic anhydride ester modifier. The mixing mode is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing; the mixing temperature is preferably 50 to 80 ℃, more preferably 60 to 70 ℃, the mixing time is not particularly limited in the invention, and the mixing is performed until the maleic anhydride is completely melted. In the present invention, the mixing order is preferably to add maleic anhydride to the sorbitan ester-based compound 1 to 15 times. 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 esterification reaction is completed, the present invention preferably further comprises cooling the obtained esterification reaction system to 30 to 40 ℃ (more preferably 32 to 38 ℃, and still more preferably 35 to 36 ℃), and the cooling manner in the present invention is not particularly limited, and may be any cooling manner known to those skilled in the art, such as natural cooling.
The invention provides a polymerized acrylic resin derivative which comprises the following preparation raw materials in parts by weight: 20 to 200 portions of acrylic acid, 0 to 2400 portions of modifier but not 0 portion, 0.1 to 20 portions of initiator and 80 to 10880 portions of water;
the modifier comprises a maleic amide modifier and/or a maleic ester modifier, and the maleic ester modifier is the maleic ester modifier in the technical scheme;
the maleic amide modifier comprises acylation products and/or hyperbranched esterification products of maleic anhydride and diethanol amine.
The preparation raw material of the polymerized acrylic resin derivative comprises 20-200 parts of acrylic acid, preferably 30-200 parts of acrylic acid, and more preferably 50-200 parts of acrylic acid.
The preparation raw material of the polymerized acrylic resin derivative comprises, by mass, 0-2400 parts of a modifier, preferably 200-2200 parts of the modifier, more preferably 300-2000 parts of the modifier, and further preferably 500-1500 parts of the modifier, wherein the modifier comprises a maleic amide modifier and/or a maleic ester modifier, and the maleic ester modifier is the maleic ester modifier in the technical scheme. In the present invention, the mass ratio of the maleic amide-based modifier to the maleic acid ester-based modifier in the modifiers is preferably (0 to 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 maleic amide-based modifier preferably comprises the steps of: mixing maleic anhydride and diethanol amine, and carrying out acylation reaction to obtain an acylation product; and (3) mixing the acylation product with an acidic catalyst, and carrying out self-esterification reaction to obtain a hyperbranched esterification product.
The method mixes maleic anhydride and diethanol amine to carry out acylation reaction to obtain the acylation product (namely, the acylation product of the maleic anhydride and the diethanol amine). 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 mixing temperature is preferably less than or equal to 45 ℃, and more preferably 20-40 ℃; the mixing time is preferably 3 to 10 hours, more preferably 5 to 8 hours. In the invention, the sequence of mixing is preferably that maleic anhydride is added into diethanol amine for mixing for 5 to 20 times; after each addition of maleic anhydride, 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 further preferably 2 to 3 hours. In the present invention, the acylation product preferably has a structural formula shown in formula III-1:
after obtaining the acylation product, the acylation product is mixed with an acid catalyst to carry out self-esterification reaction, and a hyperbranched esterification product (namely a hyperbranched esterification product of maleic anhydride and diethanol amine) is obtained. 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 not less than 98wt%. In the present invention, the solid acid preferably includes an immobilized liquid acid, an acidic oxide, a transition metal sulfide, a phosphate, a sulfate, a zeolite molecular sieve, a heteropoly acid, a cation exchange resin, a natural acidOne or more of 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 sulfide preferably includes 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 comprises one or more of ZSM-5 zeolite, X zeolite, Y zeolite, B zeolite, mordenite and aioo 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 a 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 super acid preferably includes 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%, and 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 DEG CAbout 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, during the esterification reaction, the acylation product is subjected to esterification reaction under the action of an acid catalyst to form the hyperbranched esterified polymer. After the esterification reaction is completed, the present invention preferably further comprises cooling the obtained esterification reaction system to below 100 ℃ (more preferably 20 to 40 ℃), and the cooling manner of the present invention is not particularly limited, and may be cooling manner known to those skilled in the art, such as natural cooling.
In the invention, the structural formula of the hyperbranched esterification product is preferably shown as a formula III-2:
wherein the content of the first and second substances,
represents a repeating structural unit.
The preparation raw material of the polymerized acrylic resin derivative comprises 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 weight of acrylic acid. In the invention, the initiator preferably comprises one or more of persulfate, peroxide, azo compounds 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 azodiisobutyramidine hydrochloride; the peroxides in the peroxide and peroxide-reducing agent mixture independently preferably comprise one or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, alkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, tert-butyl oxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl oxydicarbonate, dicyclohexyl peroxydicarbonate and hydrogen peroxide), the reducing agent in the peroxide-reducing agent mixture preferably comprises one or more of ferrous sulfate, cuprous sulfate, sodium bisulfite, sodium metabisulfite, sodium hydrosulfite and glucose, 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 preparation raw material of the polymeric acrylic resin derivative comprises, by mass, 80-10880 parts of water, preferably 500-10000 parts of water, more preferably 700-8000 parts of water, and even more preferably 850-6500 parts of water. In the present invention, the water is preferably distilled and/or deionized water.
The raw material for preparing the polymerized acrylic resin derivative provided by the invention preferably further comprises 5-100 parts of pH regulator, preferably 10-80 parts, more preferably 12-50 parts, and even more preferably 14-40 parts by mass of acrylic acid. In the invention, the pH regulator preferably comprises an inorganic base and/or an organic base, and the inorganic base preferably comprises one or more of sodium hydroxide, potassium hydroxide and ammonia water; the organic alkali 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 polymeric 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: and mixing the maleic amide modifier and/or the 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 polymeric acrylic resin derivative preferably comprises the steps of:
mixing the modifier with part of the 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 to carry out polymerization reaction to obtain a polymerization reaction solution;
and mixing the polymerization reaction liquid with the rest of the pH regulator and the rest of the water to obtain the polymerized acrylic resin derivative.
The invention mixes modifier and partial pH regulator to obtain modified mixed solution; the pH value of the modified mixed solution is 3-6. In the present invention, the ratio of a part of the pH adjuster to the total mass of the pH adjuster is not particularly limited, and the pH of the modified mixed solution may be adjusted to 3 to 6, and 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 deg.c, more preferably 50 to 70 deg.c. In a particular embodiment of the invention, the mixing is preferably: heating the modifier to 30-70 ℃, adding part of pH regulator to adjust the pH value to 3-6, and then continuously mixing for 30-60 min (more preferably 40-50 min). In the present invention, the pH of the modified mixed solution is more preferably 4 to 5.5, and the polymerization activity is different between different pH values, the pH is too low, and the reaction rate is slow.
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, and the polymerization reaction solution is obtained. In the present invention, the mass of the portion of water is preferably 25 to 70%, more preferably 32 to 62% of the total mass of water. The mixing mode of the invention is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing. In a particular 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 ℃), dripping an initiator aqueous solution for 5-30 min (more preferably 10 min), then dripping acrylic acid simultaneously, and continuously dripping the initiator aqueous solution for 5-30 min (more preferably 10 min) after finishing dripping the acrylic acid; the dropping time of the acrylic acid is preferably 2 to 4 hours, and 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 time for the polymerization reaction is preferably 1 to 10 hours, more preferably 2 to 5 hours.
After the polymerization reaction liquid is obtained, the polymerization reaction liquid is mixed with the rest of the pH regulator and the rest of the water to obtain the polymerized acrylic resin derivative. The mixing mode of the invention is not particularly limited, and the raw materials can be uniformly mixed, such as stirring and mixing. In a particular embodiment of the invention, the mixing is preferably: the temperature of the polymerization reaction liquid is lowered to 40 to 50 ℃ (more preferably 45 ℃), the remaining pH adjuster is added dropwise to a pH of 5 to 7 (more preferably 5 to 6.5), and then the remaining distilled water is added to mix.
The invention also provides the application of the polymerized acrylic resin derivative in the technical scheme or the application of the polymerized acrylic resin derivative prepared by the preparation method in the technical scheme as a leather assistant. In the present invention, the polymeric acrylic resin derivative is preferably used alone or in combination with other leather retanning agents as a leather retanning agent.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Adding diethanolamine into reaction equipment, slowly adding maleic anhydride for 8 times, controlling the temperature to be below 45 ℃ by ice bath, continuously adding maleic anhydride after the maleic anhydride is completely melted in the diethanolamine, continuously carrying out acylation reaction for 2 hours after the maleic anhydride is completely added for 5 hours to obtain an acylation product (N, N-dihydroxyethyl maleamic acid shown in formula III-1), then heating to 70 ℃, adding p-toluenesulfonic acid, continuously heating to 120 ℃, carrying out reaction for 2 hours, heating to 150 ℃, carrying out reaction for 1 hour, cooling to below 100 ℃, adding distilled water to adjust the solid content to be 50wt%, and obtaining a hyperbranched esterification product (shown in formula III-2). Wherein, the mol ratio of the diethanolamine to the maleic anhydride =1, and the mass of the p-toluenesulfonic acid is 1% of the total mass of the diethanolamine and the maleic anhydride.
Example 2
Adding Tween 80 into a reaction device, heating to 60 deg.C, adding maleic anhydride for 12 times, stirring until the maleic anhydride is molten, heating to 90 deg.C, reacting for 3h, and cooling to 40 deg.C to obtain maleic ester modifier (product of mixture with structure shown in formula II-4-II-7); wherein, the molar ratio of the tween 80 to the maleic anhydride is 1.5.
Example 3
Adding tween 85 into a reaction device, heating to 60 ℃, adding maleic anhydride for 10 times, stirring until the maleic anhydride is melted, continuously heating to 150 ℃, reacting for 5 hours, and cooling to 30 ℃ to obtain a maleic ester modifier (the product is shown as formula I-9, wherein a + b + c + d = 20); wherein, the molar ratio of the Tween 85 to the maleic anhydride is 1.
Example 4
Adding span 40 into a reaction device, heating to 60 ℃, adding maleic anhydride by 5 times, stirring until the maleic anhydride is molten, continuously heating to 120 ℃, reacting for 4 hours, and cooling to 40 ℃ to obtain a maleic ester modifier (the product is a mixture with a structure shown in formulas I-4-I-7); wherein the molar ratio of span 40 to maleic anhydride is 1.
Example 5
Adding 20g of the maleic amide modifier (hyperbranched esterification product) prepared in example 1 and 300g of the maleic ester modifier prepared in example 2 into a reaction device, heating to 50 ℃, adding 6g of monoethanolamine to adjust the pH value to 4.1, stirring for 30min, adding 400g of distilled water, continuing to stir for 60min, heating to 82 ℃, dropwise adding 20wt% of azodiisobutylamine hydrochloride aqueous solution (the total mass of the initiator aqueous solution is 1 g), after 10min, simultaneously starting to dropwise add 50g of acrylic acid, finishing dropwise adding 3h of acrylic acid, continuing to dropwise add the initiator aqueous solution for 10min, reacting for 3h at 85 ℃, cooling to 45 ℃, dropwise adding 8g of monoethanolamine to adjust the pH value of the system to 6.2, and slowly adding 460g of distilled water to adjust the solid content to 31wt% to obtain a polymerized acrylic resin derivative (brown viscous liquid).
Example 6
Adding 2000g of the maleic acid ester modifier prepared in the example 3 into a reaction device, heating to 70 ℃, adding 30g of sodium hydroxide to adjust the pH value to 5.3, stirring for 60min, adding 2000g of distilled water, continuing to stir for 60min, heating to 90 ℃, dropwise adding 25wt% of sodium persulfate aqueous solution (the total mass of the initiator aqueous solution is 10 g) for 10min, simultaneously dropwise adding 20g of acrylic acid, completing dripping of acrylic acid for 2h, continuously dropwise adding the initiator aqueous solution for 10min, reacting at 90 ℃ for 3h, cooling to 50 ℃, adding 5g of sodium hydroxide to adjust the pH value of the system to 5.7, slowly adding 4165g of distilled water to adjust the pH value to 25.3wt%, and obtaining the polymerized acrylic resin derivative (brown viscous liquid with solid content).
Example 7
Adding 500g of the maleate modifier prepared in the example 4 into a reaction device, heating to 70 ℃, adding 20g of 17wt% ammonia water to adjust the pH value to 4.7, stirring for 60min, adding 1000g of distilled water, continuing to stir for 30min, heating to 80 ℃, dropwise adding 25wt% ammonium persulfate aqueous solution (the total mass of the initiator aqueous solution is 3 g) for 10min, simultaneously dropwise adding 200g of acrylic acid, dropwise adding acrylic acid for 4h, then continuously dropwise adding the initiator aqueous solution for 10min, reacting for 3h at 88 ℃, cooling to 48 ℃, adding 10g of 17wt% ammonia water to adjust the pH value of the system to 6.1, and slowly adding 630g of distilled water to adjust the solid content to 31wt% to obtain a polymerized acrylic resin derivative (brown viscous liquid).
Comparative example 1
Aqueous polymeric acrylic resin LEATAN R12 (Qinhei thick chemical Co., ltd.).
Application example 1
Taking 4 pieces of the same part of cow leather wet blue, adding 0.2% of a degreasing agent FB (Qihe Gao chemical Co., ltd.) and 0.5% of oxalic acid, rotating for 2h at 40 ℃, draining, adding 100% of water, adding 4% of chromium powder for retanning for 6h, draining, adding 1.2% of sodium bicarbonate and 1% of sodium formate for neutralization, entering a retanning process, respectively adding 15% of retanning agents (the retanning agents are respectively the polymerized acrylic resin derivatives prepared in examples 5-7 and the aqueous polymerized acrylic resin LEATAN R12 of comparative example 1) in the retanning process, treating for 1.5h in a rotary drum at 35 ℃, draining, adding the same amount of a universal fatliquor BUXOM SS (manufactured by Qihe Gao chemical Co., ltd.) in the same amount, treating for 1h in the rotary drum at 50 ℃, then adding 1.2% of formic acid in the mass of the blue for fixation, diluting the formic acid with three times of water, drying at intervals of 10min each time, taking out after washing with water, testing the constant humidity at 70 ℃, and placing the leather treated under the condition of constant humidity of 10 kPa for drying at room temperature and weighing the leather until the constant humidity is reached the room temperature (after drying), and weighing, and then placing the leather is dried, and placing the leather after the leather is dried, and the leather is placed under the constant humidity after being dried Tare weight ) Then dried at the constant temperature of 60 ℃ to constant weight and weighed (recorded as m) Dry tare weight ) Moisture retention rate = m Dry tare weight /m Tare weight X 100% and the results are shown in Table 3. The mass percentages are calculated by the mass of the wet blue leather.
Table 3 application effects of leather assistants provided in examples 5 to 7 and comparative example 1
| Retanning agent | Tare weight/g | Dry tare weight/g | Moisture retention rate% | Softness | Fineness of grain surface |
| Example 5 | 718.3 | 449.9 | 62.64 | 2.573 | Refining |
| Example 6 | 740.6 | 473.5 | 63.93 | 2.514 | Refinement of |
| Example 7 | 663.5 | 386.3 | 58.22 | 2.455 | Refinement of |
| Comparative example 1 | 691.9 | 361.3 | 52.22 | 2.064 | Is thinnerTo make |
As can be seen from table 1, the moisture retention rate of the leather treated with the polyacrylic resin derivative provided by the present invention is 58.22% or more, and the polyacrylic resin derivative provided by the present invention can significantly improve the moisture retention performance of the leather.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A maleic acid ester modifier is characterized in that the maleic acid ester modifier is obtained by esterification reaction of maleic anhydride and sorbitan ester compounds;
the product of the esterification reaction comprises at least one of compounds having the structures shown in formula I and formula II:
in the formula I, R 1 including-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 including-O (OCH) 2 CH 2 ) c OOC、-O(OCH 2 CH 2 ) c OC-CH = CH-COOH or-CH 3 ；R 5 including-O (OCH) 2 CH 2 ) b H or-O (OCH) 2 CH 2 ) b OC-CH＝CH-COOH；R 6 including-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, an oleic acid group, a lauric acid group or a palmitic acid group, and a-d are independently integers.
2. The maleate ester modifier of claim 1 wherein 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.
3. The maleate ester modifier of claim 1 or 2 wherein the molar ratio of maleic anhydride to sorbitan ester compound is 1: (0.5-3).
4. The maleate modifier of claim 1 or 2 wherein the esterification reaction is carried out at a temperature of 80-150 ℃ for a period of 3-5 hours.
5. A polymerized acrylic resin derivative comprises the following preparation raw materials in parts by mass: 20-200 parts of acrylic acid, 0-2400 parts but not 0 part of modifier, 0.1-20 parts of initiator and 80-10880 parts of water;
the modifier comprises a maleic amide modifier and/or a maleic ester modifier, and the maleic ester modifier is the maleic ester modifier in any one of claims 1-4;
the maleic amide modifier comprises acylation products and/or hyperbranched esterification products of maleic anhydride and diethanol amine.
6. The polymeric acrylic resin derivative according to claim 5, wherein the method for preparing the maleic amide-based modifier comprises the steps of;
mixing maleic anhydride and diethanol amine, and carrying out acylation reaction to obtain an acylation product;
and mixing the acylation product with an acidic catalyst, and carrying out self-esterification reaction to obtain a hyperbranched esterification product.
7. The polymerized acrylic resin derivative of claim 6 wherein 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, acidic oxide, transition metal sulfide, phosphate, sulfate, zeolite molecular sieve, heteropoly acid, cation exchange resin, natural clay mineral and solid super acid.
8. The polymerized acrylic resin derivative according to claim 5 or 6, wherein the modifier comprises a maleic amide-based modifier and a maleic acid ester-based modifier in a mass ratio of (0 to 400): (0 to 2000).
9. The method for preparing a polymerized acrylic resin derivative according to any one of claims 5 to 8, comprising the steps of:
and mixing the maleic amide modifier and/or the maleic acid ester modifier with water, an initiator and acrylic acid, and carrying out polymerization reaction to obtain the polymerized acrylic resin derivative.
10. Use of the polymeric acrylic resin derivative according to any one of claims 5 to 8 or the polymeric acrylic resin derivative prepared by the preparation method according to claim 9 as a leather assistant.
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