CN102558423B - Crylic acid type macromolecule formaldehyde catching agent with retanning filling functions and preparation method thereof - Google Patents
Crylic acid type macromolecule formaldehyde catching agent with retanning filling functions and preparation method thereof Download PDFInfo
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- CN102558423B CN102558423B CN201110436865.9A CN201110436865A CN102558423B CN 102558423 B CN102558423 B CN 102558423B CN 201110436865 A CN201110436865 A CN 201110436865A CN 102558423 B CN102558423 B CN 102558423B
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Abstract
The invention relates to the technical field of leather chemical materials preparation, in particular to a crylic acid type macromolecule formaldehyde catching agent with retanning filling functions and applied to leather and a preparation method thereof. The macromolecule formaldehyde catching agent is prepared in emulsion polymerization mode with crylic acid and a derivant of the crylic acid as raw materials. The preparation method of the macromolecule formaldehyde catching agent with retanning filling functions for leather includes first selecting active hydrogen compound ethyl acetoacetate capable of conducting irreversible reaction with formaldehyde, enabling the ethyl acetoacetate to conduct ester exchange reaction with acrylic hydroxyl ethyl to combine a monomer with a double bond active hydrogen function, utilizing persulfate as an initiator, adding crylic acid and the derivant of the crylic acid to conduct emulsion polymerization reaction with the function monomer and obtaining emulsion with proper molecular weight and size distribution by control of reasonable raw material proportioning and the polymerization process.
Description
Technical field
The invention belongs to Leather Chemicals preparing technical field, be specifically related to a kind of for thering is polymer formaldehyde-trapping agent of retanning filling function and preparation method thereof.
Background technology
Formaldehyde is a kind of colourless, gas of having intense stimulus stink, very easily water-soluble, and human body is had to strong impulse effect, and serious caused people headache, blind, expiratory dyspnea, even bring out cancer.Therefore many developed countries have proposed strict limit standard to the free formaldehyde content in leather and fur product.As european union directive 2002/231/EC regulation, leatherware Free-formaldehyde content must not be greater than 150 mg/Kg.2008, national quality supervising and quarantining general bureau of China issues urgent message, require the check to listing all import and export leathers, fur and goods thereof in " goods catalogue of passing in and out that entry and exit inspection and quarantine bureau is implemented inspection and quarantine " in, increase by two projects such as forbidding azoic dyestuff and formaldehyde, the product of disqualified upon inspection does not allow to import and export.China's Ecology Leather requires directly and the leather free formaldehyde content of skin contact must not exceed 75mg/Kg, and leather free formaldehyde content not direct and skin contact must not exceed 150mg/Kg, and leather free formaldehyde content for baby must not exceed 20mg/Kg.
Urea, starch, trimeric cyanamide, polyvinyl alcohol, sulphite and superoxide etc. have certain formaldehyde catching effect, but are used on leather, and aldehydes removal effect is not obvious.The formaldehyde-trapping agent overwhelming majority of selling on domestic crust market at present, is micromolecular ammonia or amino derivative.In formaldehyde catching process, if overdose uses such formaldehyde-trapping agent, will make the formaldehyde content in leather be down in a certain limit range, generally can reduce by 50% left and right.But such formaldehyde-trapping agent is because molecular weight is little, be easy to infiltrate in hide fiber but also easily water-washed away, this has not only increased the COD in waste water, has increased intractability, and for leatherware display with use procedure in the free formaldehyde that continues to discharge do not catch effect.Therefore, leather technology worker has developed macromolecular Ammonia formaldehyde-trapping agent, hold amino dendritic formaldehyde-trapping agent and the formaldehyde-trapping agent of preparing as raw material to discard collagenic hydrolysate as having, wish that this product can play the effect that catches formaldehyde, can be combined with hide fiber again and play certain retanning filling effect (Qiang Xihuai, Tian Ling, Chen Guoping, Deng. hold the research of amino PAMAM Capturing Ability of Free-formaldehyde in Leather ability. Chinese leather. 2007,36,22-24.).But amino and formaldehyde reaction is a kind of reversible reaction, can discharge under certain conditions free formaldehyde, therefore, is filled in the likely release formaldehyde of formaldehyde-trapping agent of intracutaneous, causes the free formaldehyde content in leatherware to exceed standard.Therefore, adopt formaldehyde to react and carry out the formaldehyde-trapping agent that the principle of aldehydes removal is prepared from amino, no matter molecular size is all improper.
Chemical substance and formaldehyde that dimethyl malonate and methyl aceto acetate etc. contain reactive hydrogen (α-H) have higher reactive behavior, and react irreversible.In recent years, there is scholar to prepare hyperbranched polymer formaldehyde-trapping agent (Wang Xuechuan take dimethyl malonate as raw material according to this feature, Yuan Xuzheng, torrential by force, Deng. the synthetic and application of active methylene group class hyperbranched polymer formaldehyde-trapping agent. Chinese leather. 2008,37,43-49.).But hyperbranched polymerization need to be take high boiling organic solvent as medium, and temperature of reaction is high, and atom utilization is low, and organic solvent is difficult to deviate from, and the molecular weight of hyperbranched polymer is lower, only has 2000 left and right.Although therefore such formaldehyde-trapping agent has the effect of higher seizure formaldehyde, but still is difficult to fixedly secure in hide fiber, can water-washed away, increase the weight of the processing load of waste water.
Retanning is the important procedure in leather manufacture process, and acrylic retanning agents is a kind of retanning filler of large usage quantity in leather manufacture, carboxyl on acrylic resin macromolecule side chain can with collagen peptide chain on multiple group and the chromic salts generation Chemical bond in chrome tanned leather, be the high molecular retanning agent that a kind of binding ability is strong, filling effect is good.
Summary of the invention
The problem existing based on prior art, the object of this invention is to provide a kind of acrylic type polymer formaldehyde-trapping agent with retanning filling function and preparation method thereof.This polymer formaldehyde-trapping agent is to be combined by the multiple group on collegen filament based on acrylic acid double tanning agent, the feature in the leather that can firmly fix, thus the active hydrogen group with aldehydes removal function is firmly fixed in leather.So not only realize the free formaldehyde in the irreversible long-term removal leather of product, realize the environmental protection of leather products; And leather is also had to good retanning and filling effect, can save the usage quantity of other Retanning Materials.
To achieve the above object of the invention, the technical solution adopted in the present invention is: a kind of acrylic type polymer formaldehyde-trapping agent with retanning filling function is provided, it is characterized in that: each component in described product and mass parts thereof are than as follows:
Active hydrogen function monomer 20-50 part;
Vinylformic acid 150-250 part;
Ethyl propenoate 20-50 part;
Methacrylic acid hexadecyl ester 10-30 part;
Ammonium persulphate 1-4 part;
N-dodecyl mercaptan 1-5 part;
Sodium bicarbonate 0.2-0.8 part;
Sodium hydroxide 20-40 part;
Sodium lauryl sulphate 2-5 part;
Isomery alcohol ether TO-8 1-4 part;
Deionized water 600-1000 part.
Each component in above-mentioned active hydrogen function monomer and mass parts thereof are than as follows:
Hydroxyethyl acrylate 300-500 part;
Methyl aceto acetate 600-800 part;
Tosic acid 0.5-2 part;
Nitroxyl free radical piperidine alcohols 0.5-5.0 part.
The chemical structural formula of the above-mentioned function monomer containing reactive hydrogen is:
When concrete enforcement, the described monomer with retanning function is vinylformic acid and acrylate, the monomer with function of removing formaldehyde is the autonomous synthetic polymerisable function monomer containing reactive hydrogen, initiator is ammonium persulphate, molecular weight regulator is positive Dodecyl Mercaptan, buffer reagent is sodium bicarbonate, and anionic emulsifier is sodium lauryl sulphate, and nonionic emulsifying agent is isomery alcohol ether TO-8.
When concrete enforcement, there is retanning and fill the polymer formaldehyde-trapping agent of function, wherein contain the function monomer of reactive hydrogen synthetic in, tosic acid is the catalyzer of reaction, nitroxyl free radical piperidine alcohols is stopper.
A preparation method for the above-mentioned polymer formaldehyde-trapping agent with retanning filling function, is characterized in that, described preparation method comprises the steps:
Synthesizing of A, polymerisable reactive hydrogen monomer: Hydroxyethyl acrylate 300-500 part and methyl aceto acetate 600-800 part are mixed, then add tosic acid 0.5-2 part, nitroxyl free radical piperidine alcohols 0.5-5.0 part, react after 4 hours at 100-140 ℃, make and contain active hydrogen function monomer, cooling stand-by;
B, pre-emulsification: to the deionized water that drops into the ionized water total mass 40%-50% that accounts in emulsifying kettle, in emulsifying agent, account for the sodium lauryl sulphate of sodium lauryl sulphate total mass 50%-80%, account for isomery alcohol ether TO-8 and the whole monomer of isomery alcohol ether TO-8 total mass 60%-90%, stirring and emulsifying 25-35 minute, forms pre-emulsion;
C, polyreaction: to the deionized water that drops into the ionized water total mass 30%-50% that accounts in polymeric kettle, remaining sodium lauryl sulphate and isomery alcohol ether TO-8 in emulsifying agent, buffer reagent, molecular weight regulator, stir and heat up, when temperature reaches after 75 ℃, adding the initiator that accounts for initiator total mass 20%-40%, first initiator should use deionized water dissolving, forms the initiator solution of 5-10% mass concentration.After 10 minutes, start to drip respectively pre-emulsion and initiator solution, approximately after 5-20 minute, polyreaction starts, and can acutely heat up, and maintains emulsion temperature at 85 ℃, the time for adding of pre-emulsion is controlled at 2-4 hour, and initiator solution should be later than pre-emulsion and add for 0.5 hour;
D, insulation: after initiator solution is added dropwise to complete, temperature is raised to 90 ℃, insulation reaction 0.5-1 hour;
E, neutralization: after insulation reaction completes, cool to below 45 ℃, the aqueous sodium hydroxide solution that is 20% by mass concentration is adjusted to the pH value of emulsion between 5.5-6.5, filter discharging, obtains having the polymer formaldehyde-trapping agent finished product of retanning filling function.
When concrete enforcement, the solid content of test emulsion sampling is 20%-30%, is qualified.
The present invention has following features
1. reactive hydrogen monomer disclosed in this invention has the irreversible function of removing formaldehyde that goes, though there is similar report, but adopt transesterification reaction to synthesize a kind of special esters of acrylic acid function monomer that contains reactive hydrogen structure, and be aggregated on acrylic molecules chain, generate macromolecular structure, still belong to the first time.
2. adopt this function monomer and vinylformic acid, acrylic ester monomer carries out emulsion polymerization, drips the enforcement of technique by the whole process of rational proportioning raw materials and pre-emulsion, obtains the emulsion with suitable molecular weight and uniform grading distribution.Carboxyl in vinylformic acid has guaranteed to have stronger binding ability with leather; what molecular weight and emulsion particle diameter distributed evenly makes product have good perviousness and fillibility to leather; special reactive hydrogen structure can irreversible removal formaldehyde, realizes the environmental protection of leather products.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjust according to the content of the invention described above and all should belong to protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Embodiment 1:
The first step, contains the synthetic of active hydrogen function monomer:
400 parts of Hydroxyethyl acrylates are mixed with 800 parts of methyl aceto acetates, then add 1 part of tosic acid, 2 parts of nitroxyl free radical piperidine alcohols, after 4 hours, make the function monomer that contains reactive hydrogen structure 120 ℃ of reactions, cooling stand-by.
Second step, has the preparation of the acrylic type polymer formaldehyde-trapping agent of retanning filling function
Adopt following formula:
Active hydrogen function monomer, 40 parts; Vinylformic acid, 200 parts; Ethyl propenoate, 30 parts; Methacrylic acid hexadecyl ester, 20 parts; Ammonium persulphate, 2 parts; N-dodecyl mercaptan, 1.5 parts; Sodium bicarbonate, 0.3 part; Sodium hydroxide, 30 parts; Sodium lauryl sulphate, 3 parts; Isomery alcohol ether TO-8,1.5 parts; Deionized water, 775 parts.
Employing is prepared as follows method:
(1) pre-emulsification: drop into 300 parts of deionized waters in emulsifying kettle, 2 parts of sodium lauryl sulphate, 1 part of isomery alcohol ether TO-8,40 parts of active hydrogen function monomers, 200 parts of vinylformic acid, 30 parts of ethyl propenoates, 20 parts of methacrylic acid hexadecyl esters, stirring and emulsifying 30 minutes, forms pre-emulsion;
(2) polyreaction: drop into 317 parts of deionized waters in polymerization reaction kettle, 1 part of sodium lauryl sulphate, 0.5 part of isomery alcohol ether TO-8,0.3 part of sodium bicarbonate, 1.5 parts of n-dodecyl mercaptans, stir and heat up, when temperature reaches after 75 ℃, add 12 parts of ammonium persulfate solutions (be made into the initiator solution of 5% mass concentration with deionized water, 2 parts of ammonium persulphates are dissolved in 38 parts of deionized waters); After 10 minutes, start to drip respectively pre-emulsion and remaining 28 parts of initiator solutions, approximately after 5-20 minute, polyreaction starts, and can acutely heat up, and maintains emulsion temperature at 85 ℃, the time for adding of pre-emulsion is controlled at 3 hours, and initiator solution should be later than pre-emulsion and add for 0.5 hour;
(3) insulation: after initiator solution is added dropwise to complete, temperature is raised to 90 ℃, insulation reaction 0.5 hour;
(4) neutralization: after insulation reaction completes, cool to below 45 ℃, drip the pH value that the aqueous sodium hydroxide solution that 150 parts of mass concentrations are 20% (being about to 30 parts of sodium hydroxide is dissolved in 120 parts of deionized waters) regulates emulsion, the ph value of emulsion in polymerization reaction kettle is adjusted to 6.0 left and right.It is qualified that sampling and testing solid content is that 30% left and right is, and filters discharging, obtains having retanning and fill the polymer formaldehyde-trapping agent finished product of function.
Embodiment 2:
The first step, contains the synthetic of active hydrogen function monomer:
300 parts of Hydroxyethyl acrylates are mixed with 650 parts of methyl aceto acetates, then add 0.8 part of tosic acid, 2 parts of nitroxyl free radical piperidine alcohols, after 4 hours, make the function monomer that contains reactive hydrogen structure 120 ℃ of reactions, cooling stand-by.
Second step, has the preparation of the acrylic type polymer formaldehyde-trapping agent of retanning filling function
Adopt following formula:
Active hydrogen function monomer, 30 parts; Vinylformic acid, 150 parts; Ethyl propenoate, 30 parts; Methacrylic acid hexadecyl ester, 20 parts; Ammonium persulphate, 1.8 parts; N-dodecyl mercaptan, 1.5 parts; Sodium bicarbonate, 0.3 part; Sodium hydroxide, 25 parts; Sodium lauryl sulphate, 3 parts; Isomery alcohol ether TO-8,1.5 parts; Deionized water, 750 parts.
Employing is prepared as follows method:
(1) pre-emulsification: drop into 350 parts of deionized waters in emulsifying kettle, 2 parts of sodium lauryl sulphate, 1 part of isomery alcohol ether TO-8,30 parts of active hydrogen function monomers, 150 parts of vinylformic acid, 30 parts of ethyl propenoates, 20 parts of methacrylic acid hexadecyl esters, stirring and emulsifying 30 minutes, forms pre-emulsion;
(2) polyreaction: drop into 262 parts of deionized waters in polymerization reaction kettle, 1 part of sodium lauryl sulphate, 0.5 part of isomery alcohol ether TO-8,0.3 part of sodium bicarbonate, 1.5 parts of n-dodecyl mercaptans, stir and heat up, when temperature reaches after 75 ℃, add 12 parts of ammonium persulfate solutions (be made into the initiator solution of 5% mass concentration with deionized water, 2 parts of ammonium persulphates are dissolved in 38 parts of deionized waters); After 10 minutes, start to drip respectively pre-emulsion and remaining 28 parts of initiator solutions, approximately after 5-20 minute, polyreaction starts, and can acutely heat up, and maintains emulsion temperature at 85 ℃, the time for adding of pre-emulsion is controlled at 2.5 hours, and initiator solution should be later than pre-emulsion and add for 0.5 hour;
(3) insulation: after initiator solution is added dropwise to complete, temperature is raised to 90 ℃, insulation reaction 0.5 hour;
(4) neutralization: after insulation reaction completes, cool to below 45 ℃, drip the pH value that the aqueous sodium hydroxide solution that 125 parts of mass concentrations are 20% (being about to 25 parts of sodium hydroxide is dissolved in 100 parts of deionized waters) regulates emulsion, the ph value of emulsion in polymerization reaction kettle is adjusted to 6.0 left and right.It is qualified that sampling and testing solid content is that 26% left and right is, and filters discharging, obtains having retanning and fill the polymer formaldehyde-trapping agent finished product of function.
Embodiment 3:
The first step, contains the synthetic of active hydrogen function monomer:
400 parts of Hydroxyethyl acrylates are mixed with 750 parts of methyl aceto acetates, then add 1 part of tosic acid, 2 parts of nitroxyl free radical piperidine alcohols, after 4 hours, make the function monomer that contains reactive hydrogen structure 120 ℃ of reactions, cooling stand-by.
Second step, has the preparation of the acrylic type polymer formaldehyde-trapping agent of retanning filling function
Adopt following formula:
Active hydrogen function monomer, 20 parts; Vinylformic acid, 150 parts; Ethyl propenoate, 20 parts; Methacrylic acid hexadecyl ester, 10 parts; Ammonium persulphate, 1.5 parts; N-dodecyl mercaptan, 1.2 parts; Sodium bicarbonate, 0.3 part; Sodium hydroxide, 25 parts; Sodium lauryl sulphate, 2.5 parts; Isomery alcohol ether TO-8,1.5 parts; Deionized water, 928 parts.
Employing is prepared as follows method:
(1) pre-emulsification: drop into 450 parts of deionized waters in emulsifying kettle, 1.5 parts of sodium lauryl sulphate, 1 part of isomery alcohol ether TO-8,20 parts of active hydrogen function monomers, 150 parts of vinylformic acid, 20 parts of ethyl propenoates, 10 parts of methacrylic acid hexadecyl esters, stirring and emulsifying 30 minutes, forms pre-emulsion;
(2) polyreaction: drop into 349.5 parts of deionized waters in polymerization reaction kettle, 1 part of sodium lauryl sulphate, 0.5 part of isomery alcohol ether TO-8,0.3 part of sodium bicarbonate, 1.2 parts of n-dodecyl mercaptans, stir and heat up, when temperature reaches after 75 ℃, add 6 parts of ammonium persulfate solutions (be made into the initiator solution of 5% mass concentration with deionized water, 1.5 parts of ammonium persulphates are dissolved in 28.5 parts of deionized waters); After 10 minutes, start to drip respectively pre-emulsion and remaining 24 parts of initiator solutions, approximately after 5-20 minute, polyreaction starts, and can acutely heat up, and maintains emulsion temperature at 85 ℃, the time for adding of pre-emulsion is controlled at 2.5 hours, and initiator solution should be later than pre-emulsion and add for 0.5 hour;
(3) insulation: after initiator solution is added dropwise to complete, temperature is raised to 90 ℃, insulation reaction 0.5 hour;
(4) neutralization: after insulation reaction completes, cool to below 45 ℃, drip the pH value that the aqueous sodium hydroxide solution that 125 parts of mass concentrations are 20% (being about to 25 parts of sodium hydroxide is dissolved in 100 parts of deionized waters) regulates emulsion, the ph value of emulsion in polymerization reaction kettle is adjusted to 6.0 left and right.It is qualified that sampling and testing solid content is that 20% left and right is, and filters discharging, obtains having retanning and fill the polymer formaldehyde-trapping agent finished product of function.
Claims (2)
1. have retanning and fill the preparation method of the acrylic type polymer formaldehyde-trapping agent of function, it is characterized in that, each component in described product and mass parts thereof are than as follows:
Active hydrogen function monomer 20-50 part;
Vinylformic acid 150-250 part;
Ethyl propenoate 20-50 part;
Methacrylic acid hexadecyl ester 10-30 part;
Ammonium persulphate 1-4 part;
N-dodecyl mercaptan 1-5 part;
Sodium bicarbonate 0.2-0.8 part;
Sodium hydroxide 20-40 part;
Sodium lauryl sulphate 2-5 part;
Isomery alcohol ether TO-8 1-4 part;
Deionized water 600-1000 part;
Described preparation method comprises the steps:
Synthesizing of A, polymerisable active hydrogen function monomer: Hydroxyethyl acrylate 300-500 part and methyl aceto acetate 600-800 part are mixed, then add tosic acid 0.5-2 part, nitroxyl free radical piperidine alcohols 0.5-5.0 part, react after 4 hours at 100-140 ℃, make and contain active hydrogen function monomer, cooling stand-by;
B, pre-emulsification: to the deionized water that drops into the ionized water total mass 40%-50% that accounts in emulsifying kettle, in emulsifying agent, account for the sodium lauryl sulphate of sodium lauryl sulphate total mass 50%-80%, account for isomery alcohol ether TO-8 and the whole monomer of isomery alcohol ether TO-8 total mass 60%-90%, stirring and emulsifying 25-30 minute, forms pre-emulsion;
C, polyreaction: to the deionized water that drops into the ionized water total mass 30%-50% that accounts in polymeric kettle, remaining sodium lauryl sulphate and isomery alcohol ether TO-8 in emulsifying agent, sodium bicarbonate, n-dodecyl mercaptan, stir and heat up, when temperature reaches after 75 ℃, add the ammonium persulphate that accounts for ammonium persulphate total mass 20%-40%, first ammonium persulphate should use deionized water dissolving, form the ammonium persulfate solution of 5-10% mass concentration, after 10 minutes, start to drip respectively pre-emulsion and remaining ammonium persulfate solution, after 5-20 minute, polyreaction starts, can violently heat up, maintain emulsion temperature at 85 ℃, the time for adding of pre-emulsion is controlled at 2-4 hour, ammonium persulfate solution should be later than pre-emulsion and add for 0.5 hour,
D, insulation: after ammonium persulfate solution is added dropwise to complete, temperature is raised to 90 ℃, insulation reaction 0.5-1 hour;
E, neutralization: after insulation reaction completes, cool to below 45 ℃, the aqueous sodium hydroxide solution that is 20% by mass concentration is adjusted to the pH value of emulsion between 5.5-6.5, filter discharging, obtains having the polymer formaldehyde-trapping agent finished product of retanning filling function.
2. preparation method as described in claim 1, is characterized in that, the solid content of test emulsion sampling is 20%-30%, is qualified.
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| CN104645800B (en) * | 2013-11-25 | 2016-08-17 | 北京市理化分析测试中心 | formaldehyde catching agent and preparation method thereof |
| CN104060001B (en) * | 2014-07-10 | 2016-01-13 | 北京泛博科技有限责任公司 | A kind of de-aldehyde agent and preparation method thereof |
| EP3330307A1 (en) * | 2016-12-05 | 2018-06-06 | Covestro Deutschland AG | Use of acrylic acid esters and amides for reducing emissions of a polyurethane foam |
| CN106823237A (en) * | 2017-01-26 | 2017-06-13 | 南京双全科技有限公司 | Except formaldehyde smoke agent and preparation method thereof |
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