CN102558423A - 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
- Publication number
- CN102558423A CN102558423A CN2011104368659A CN201110436865A CN102558423A CN 102558423 A CN102558423 A CN 102558423A CN 2011104368659 A CN2011104368659 A CN 2011104368659A CN 201110436865 A CN201110436865 A CN 201110436865A CN 102558423 A CN102558423 A CN 102558423A
- Authority
- CN
- China
- Prior art keywords
- function
- emulsion
- retanning
- formaldehyde
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
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 the leather chemical industry technical field of material, be specifically related to a kind ofly be used to have retanning and fill polymer formaldehyde-trapping agent of function and preparation method thereof.
Background technology
Formaldehyde is a kind of colourless, gas that the intense stimulus stink is arranged, and is very easily water-soluble, and human body is had the strong impulse effect, 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 the fur product.Like european union directive 2002/231/EC regulation, the leatherware free formaldehyde content must not be greater than 150 mg/Kg.2008; China national quality supervision quarantine general bureau issue urgent message; Requirement is imported and exported the check of leather, fur and goods thereof to all that list in " goods catalogue of passing in and out that entry and exit inspection and quarantine bureau is implemented inspection and quarantine "; Increase by two projects such as forbidding azoic dyestuff and formaldehyde, the product of disqualified upon inspection does not allow to import and export.The ecological leather of China requires directly and the leather free formaldehyde content of skin exposure must not surpass 75mg/Kg, and leather free formaldehyde content not direct and skin exposure must not surpass 150mg/Kg, and leather free formaldehyde content for baby must not surpass 20mg/Kg.
Urea, starch, trimeric cyanamide, polyvinyl alcohol, sulphite and superoxide etc. all have certain formaldehyde catching effect, but are used on the leather, and the aldehydes removal effect is not obvious.The formaldehyde-trapping agent overwhelming majority of selling on the domestic crust market at present, is micromolecular ammonia or amino verivate.In the formaldehyde catching process, if overdose uses such formaldehyde-trapping agent, the formaldehyde content in the leather is reduced in a certain limit range, generally can reduce about 50%.But such formaldehyde-trapping agent is because molecular weight is little; Be easy to infiltrate in the hide fiber but also water-washed away easily; This has not only increased the COD in the waste water, has increased intractability, and for leatherware display with use in the not seizure effect of free formaldehyde that continues to discharge.Therefore; The leather technology worker has developed macromolecular Ammonia formaldehyde-trapping agent, as has the amino dendritic formaldehyde-trapping agent of end and be the formaldehyde-trapping agent of feedstock production with discarded collagenic hydrolysate, hopes that this product can play the effect of catching formaldehyde; Can combine to play certain retanning filling effect (Qiang Xihuai again with hide fiber; Tian Ling, Chen Guoping, etc. hold amino PAMAM dendrimer to catch free formaldehyde Research on ability in the leather. Chinese leather. 2007; 36,22-24.).But amino and formolite reaction is a kind of reversible reaction, can discharge free formaldehyde under certain conditions, therefore, is filled in the possible release formaldehyde of formaldehyde-trapping agent of intracutaneous, causes the free formaldehyde content in the leatherware to exceed standard.Therefore, the formaldehyde-trapping agent that the principle that adopts formaldehyde and amino reaction to carry out aldehydes removal is prepared from, no matter molecular size is all improper.
Methyl-malonate and methyl aceto acetate etc. contain reactive hydrogen, and (chemical substance and the formaldehyde of α-H) have high reaction activity and high, and react irreversible.In recent years; The scholar is arranged according to these characteristics hyperbranched polymer formaldehyde-trapping agent (Wang Xuechuan that has been feedstock production with the methyl-malonate; Yuan Xuzheng, torrential by force, etc. the synthetic and application of active methylene base class hyperbranched polymer formaldehyde-trapping agent. Chinese leather. 2008; 37,43-49.).But hyperbranched polymerization need be a medium with high boiling organic solvent, 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 about 2000.Though therefore such formaldehyde-trapping agent has the effect of higher seizure formaldehyde, but still is difficult to fixedly secure in hide fiber,, increased the weight of the processing burden of waste water can water-washed away.
Retanning is the important procedure in the leather manufacturing processed; And the acrylic acid or the like retanning agent is a kind of retanning filler of large usage quantity in the leather manufacturing; Carboxyl on the vinyl resin macromolecule side chain can with multiple group on the collagen peptide chain and the chromic salts generation Chemical bond in the 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
Based on the problem that prior art exists, the purpose of this invention is to provide a kind of acrylic type polymer formaldehyde-trapping agent and preparation method thereof with retanning filling function.This polymer formaldehyde-trapping agent is based on acrylic acid double tanning agent and can combines with the multiple group on the collegen filament, the characteristics in the leather that can firmly fix, thereby firm being fixed in the leather of active hydrogen group that will have the aldehydes removal function.So not only realize the free formaldehyde in the irreversible secular removal leather of product, realize the environmental protectionization of leather products; And leather also had good retanning and filling effect, can save the usage quantity of other retanning materials.
For reaching the foregoing invention purpose, the technical scheme that the present invention adopted is: a kind of acrylic type polymer formaldehyde-trapping agent that function is filled in retanning that has is provided, it is characterized in that: each component in the said product and mass parts thereof are such as shown in down:
Active hydrogen function monomer 20-50 part;
Vinylformic acid 150-250 part;
Ethyl propenoate 20-50 part;
Methylacrylic acid hexadecyl ester 10-30 part;
Ammonium persulphate 1-4 part;
N-dodecyl mercaptan 1-5 part;
Sodium hydrogencarbonate 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 the above-mentioned active hydrogen function monomer and mass parts thereof are such as shown in down:
Hydroxyethyl acrylate 300-500 part;
Methyl aceto acetate 600-800 part;
Tosic acid 0.5-2 part;
NO free radical piperidines alcohol 0.5-5.0 part.
The above-mentioned chemical structural formula that contains the function monomer of reactive hydrogen is:
During practical implementation; Said monomer with retanning function is vinylformic acid and propenoate, and the monomer with function of removing formaldehyde is the polymerisable function monomer that contains reactive hydrogen of autonomous synthetic, and initiator is an ammonium persulphate; Molecular weight regulator is positive Dodecyl Mercaptan; Buffer reagent is a sodium hydrogencarbonate, and anionic emulsifier is a sodium lauryl sulphate, and nonionic emulsifying agent is isomery alcohol ether TO-8.
During practical implementation, have the polymer formaldehyde-trapping agent that function is filled in retanning, wherein contain the function monomer of reactive hydrogen synthetic in, tosic acid is a catalyst for reaction, NO free radical piperidines alcohol is stopper.
A kind of above-mentioned preparation method that the polymer formaldehyde-trapping agent of function is filled in retanning that has is characterized in that said preparation method comprises the steps:
A, polymerisable reactive hydrogen are monomeric synthetic: Hydroxyethyl acrylate 300-500 part and methyl aceto acetate 600-800 part are mixed; Add tosic acid 0.5-2 part then; NO free radical piperidines alcohol 0.5-5.0 part;, make and contain the active hydrogen function monomer after 4 hours 100-140 ℃ of reaction, cool off for use;
B, emulsification in advance: the deionized water that in the emulsification still, drops into the ionized water total mass 40%-50% that accounts for; Account for the sodium lauryl sulphate of sodium lauryl sulphate total mass 50%-80% in the emulsifying agent; Account for the isomery alcohol ether TO-8 and whole monomers of isomery alcohol ether TO-8 total mass 60%-90%; Stirring and emulsifying 25-35 minute, form pre-emulsion;
C, polyreaction: in polymeric kettle, drop into the deionized water of the ionized water total mass 30%-50% that accounts for, remaining sodium lauryl sulphate and isomery alcohol ether TO-8 in the emulsifying agent, buffer reagent; Molecular weight regulator; Stir and intensification, after temperature reaches 75 ℃, add the initiator that accounts for initiator total mass 20%-40%; Initiator should at first be used deionized water dissolving, forms the initiator solution of 5-10% mass concentration.After 10 minutes, begin to drip respectively pre-emulsion and initiator solution, approximately after 5-20 minute; Polyreaction begins, and can acutely heat up, and keeps emulsion temperature at 85 ℃; The dropping time of pre-emulsion was controlled at 2-4 hour, and initiator solution should be later than pre-emulsion and add in 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 is accomplished, cool to below 45 ℃, to use mass concentration be 20% aqueous sodium hydroxide solution is adjusted to the pH value of emulsion between the 5.5-6.5, filters discharging, promptly obtains having the polymer formaldehyde-trapping agent finished product of retanning filling function.
During practical implementation, the solid content of test emulsion sampling is 20%-30%, then is qualified.
The present invention has following characteristics
1. the disclosed reactive hydrogen monomer of the present invention has irreversible removal formaldehyde function; Though similar report is arranged; But adopt transesterification reaction to synthesize a kind of special esters of acrylic acid function monomer that contains the reactive hydrogen structure; And it is aggregated on the 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, and the whole process dropping implementation of processes through reasonable raw material proportioning and pre-emulsion obtains to have the emulsion of suitable molecular weight and uniform grading distribution.Carboxyl in the vinylformic acid has guaranteed to have stronger binding ability with leather; The product that evenly then makes that molecular weight and emulsion particle diameter distribute has good penetration property and fillibility to leather; Special reactive hydrogen structure then can irreversible removal formaldehyde, realizes the environmental protectionization of leather products.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjust and all should belong to protection scope of the present invention according to the content of the invention described above.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Embodiment 1:
The first step, it is monomeric synthetic to contain active hydrogen function:
400 parts of Hydroxyethyl acrylates and methyl aceto acetate are mixed for 800 parts, add 1 part of tosic acid then, 2 parts of NO free radical piperidines alcohol after 4 hours, make the function monomer that contains the reactive hydrogen structure 120 ℃ of reactions, cool off for use.
In second step, has the preparation that the acrylic type polymer formaldehyde-trapping agent of function is filled in retanning
Adopt following prescription:
The active hydrogen function monomer, 40 parts; Vinylformic acid, 200 parts; Ethyl propenoate, 30 parts; The methylacrylic acid hexadecyl ester, 20 parts; Ammonium persulphate, 2 parts; N-dodecyl mercaptan, 1.5 parts; Sodium hydrogencarbonate, 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) emulsification in advance: in the emulsification still, drop into 300 parts of deionized waters, 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 methylacrylic acid hexadecyl esters, stirring and emulsifying 30 minutes forms pre-emulsion;
(2) polyreaction: in polymerization reaction kettle, drop into 317 parts of deionized waters, 1 part of sodium lauryl sulphate, 0.5 part of isomery alcohol ether TO-8; 0.3 part sodium hydrogencarbonate; 1.5 part n-dodecyl mercaptan stirs and intensification, after temperature reaches 75 ℃; Add 12 parts of ammonium persulfate solutions (be made into the initiator solution of 5% mass concentration with deionized water, promptly 2 parts of ammonium persulphates are dissolved in 38 parts of deionized waters); After 10 minutes, begin to drip respectively pre-emulsion and remaining 28 parts of initiator solutions, approximately after 5-20 minute; Polyreaction begins, and can acutely heat up, and keeps emulsion temperature at 85 ℃; The dropping time of pre-emulsion was controlled at 3 hours, and initiator solution should be later than pre-emulsion and add in 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 is accomplished; Cool to below 45 ℃; Drip 150 parts of mass concentrations and be 20% aqueous sodium hydroxide solution (being about to 30 parts of sodium hydroxide is dissolved in 120 parts of deionized waters) and regulate the pH value of emulsion, the ph value of emulsion in the polymerization reaction kettle is adjusted to about 6.0.The sampling and testing solid content is about 30% to be qualified, filters discharging, promptly obtains having the polymer formaldehyde-trapping agent finished product that function is filled in retanning.
Embodiment 2:
The first step, it is monomeric synthetic to contain active hydrogen function:
300 parts of Hydroxyethyl acrylates and methyl aceto acetate are mixed for 650 parts, add 0.8 part of tosic acid then, 2 parts of NO free radical piperidines alcohol after 4 hours, make the function monomer that contains the reactive hydrogen structure 120 ℃ of reactions, cool off for use.
In second step, has the preparation that the acrylic type polymer formaldehyde-trapping agent of function is filled in retanning
Adopt following prescription:
The active hydrogen function monomer, 30 parts; Vinylformic acid, 150 parts; Ethyl propenoate, 30 parts; The methylacrylic acid hexadecyl ester, 20 parts; Ammonium persulphate, 1.8 parts; N-dodecyl mercaptan, 1.5 parts; Sodium hydrogencarbonate, 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) emulsification in advance: in the emulsification still, drop into 350 parts of deionized waters, 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 methylacrylic acid hexadecyl esters, stirring and emulsifying 30 minutes forms pre-emulsion;
(2) polyreaction: in polymerization reaction kettle, drop into 262 parts of deionized waters, 1 part of sodium lauryl sulphate, 0.5 part of isomery alcohol ether TO-8; 0.3 part sodium hydrogencarbonate; 1.5 part n-dodecyl mercaptan stirs and intensification, after temperature reaches 75 ℃; Add 12 parts of ammonium persulfate solutions (be made into the initiator solution of 5% mass concentration with deionized water, promptly 2 parts of ammonium persulphates are dissolved in 38 parts of deionized waters); After 10 minutes, begin to drip respectively pre-emulsion and remaining 28 parts of initiator solutions, approximately after 5-20 minute; Polyreaction begins, and can acutely heat up, and keeps emulsion temperature at 85 ℃; The dropping time of pre-emulsion was controlled at 2.5 hours, and initiator solution should be later than pre-emulsion and add in 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 is accomplished; Cool to below 45 ℃; Drip 125 parts of mass concentrations and be 20% aqueous sodium hydroxide solution (being about to 25 parts of sodium hydroxide is dissolved in 100 parts of deionized waters) and regulate the pH value of emulsion, the ph value of emulsion in the polymerization reaction kettle is adjusted to about 6.0.The sampling and testing solid content is about 26% to be qualified, filters discharging, promptly obtains having the polymer formaldehyde-trapping agent finished product that function is filled in retanning.
Embodiment 3:
The first step, it is monomeric synthetic to contain active hydrogen function:
400 parts of Hydroxyethyl acrylates and methyl aceto acetate are mixed for 750 parts, add 1 part of tosic acid then, 2 parts of NO free radical piperidines alcohol after 4 hours, make the function monomer that contains the reactive hydrogen structure 120 ℃ of reactions, cool off for use.
In second step, has the preparation that the acrylic type polymer formaldehyde-trapping agent of function is filled in retanning
Adopt following prescription:
The active hydrogen function monomer, 20 parts; Vinylformic acid, 150 parts; Ethyl propenoate, 20 parts; The methylacrylic acid hexadecyl ester, 10 parts; Ammonium persulphate, 1.5 parts; N-dodecyl mercaptan, 1.2 parts; Sodium hydrogencarbonate, 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) emulsification in advance: in the emulsification still, drop into 450 parts of deionized waters, 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 methylacrylic acid hexadecyl esters, stirring and emulsifying 30 minutes forms pre-emulsion;
(2) polyreaction: in polymerization reaction kettle, drop into 349.5 parts of deionized waters, 1 part of sodium lauryl sulphate, 0.5 part of isomery alcohol ether TO-8; 0.3 part sodium hydrogencarbonate; 1.2 part n-dodecyl mercaptan stirs and intensification, after temperature reaches 75 ℃; Add 6 parts of ammonium persulfate solutions (be made into the initiator solution of 5% mass concentration with deionized water, promptly 1.5 parts of ammonium persulphates are dissolved in 28.5 parts of deionized waters); After 10 minutes, begin to drip respectively pre-emulsion and remaining 24 parts of initiator solutions, approximately after 5-20 minute; Polyreaction begins, and can acutely heat up, and keeps emulsion temperature at 85 ℃; The dropping time of pre-emulsion was controlled at 2.5 hours, and initiator solution should be later than pre-emulsion and add in 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 is accomplished; Cool to below 45 ℃; Drip 125 parts of mass concentrations and be 20% aqueous sodium hydroxide solution (being about to 25 parts of sodium hydroxide is dissolved in 100 parts of deionized waters) and regulate the pH value of emulsion, the ph value of emulsion in the polymerization reaction kettle is adjusted to about 6.0.The sampling and testing solid content is about 20% to be qualified, filters discharging, promptly obtains having the polymer formaldehyde-trapping agent finished product that function is filled in retanning.
Claims (7)
1. have retanning and fill acrylic type polymer formaldehyde-trapping agent of function and preparation method thereof; Be to be that raw material adopts emulsion polymerization way to be prepared from vinylformic acid and verivate thereof, it is characterized in that: each component in the said product and mass parts thereof are such as shown in down:
Active hydrogen function monomer 20-50 part;
Vinylformic acid 150-250 part;
Ethyl propenoate 20-50 part;
Methylacrylic acid hexadecyl ester 10-30 part;
Ammonium persulphate 1-4 part;
N-dodecyl mercaptan 1-5 part;
Sodium hydrogencarbonate 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.
2. according to claim 1 have an acrylic type polymer formaldehyde-trapping agent that function is filled in retanning, it is characterized in that, each component in the said active hydrogen function monomer and mass parts thereof are such as shown in down:
Hydroxyethyl acrylate 300-500 part;
Methyl aceto acetate 600-800 part;
Tosic acid 0.5-2 part;
NO free radical piperidines alcohol 0.5-5.0 part.
3. the acrylic type polymer formaldehyde-trapping agent with retanning filling function according to claim 1 and 2 is characterized in that the monomeric chemical structural formula of said active hydrogen function is:
4. the acrylic type polymer formaldehyde-trapping agent with retanning filling function according to claim 1 is characterized in that said monomer with retanning function is vinylformic acid and propenoate; Monomer with function of removing formaldehyde is the polymerisable function monomer that contains reactive hydrogen of autonomous synthetic; Initiator is an ammonium persulphate, and molecular weight regulator is positive Dodecyl Mercaptan, and buffer reagent is a sodium hydrogencarbonate; Anionic emulsifier is a sodium lauryl sulphate, and nonionic emulsifying agent is isomery alcohol ether TO-8.
5. according to claim 2 have an acrylic type polymer formaldehyde-trapping agent that function is filled in retanning, wherein contain the function monomer of reactive hydrogen synthetic in, tosic acid is a catalyst for reaction, NO free radical piperidines alcohol is stopper.
6. according to described acrylic type polymer formaldehyde-trapping agent of arbitrary claim of claim 1 to 5 and preparation method thereof, it is characterized in that said preparation method comprises the steps: with retanning filling function
A, polymerisable reactive hydrogen are monomeric synthetic: Hydroxyethyl acrylate 300-500 part and methyl aceto acetate 600-800 part are mixed; Add tosic acid 0.5-2 part then; NO free radical piperidines alcohol 0.5-5.0 part; After 4 hours, make the function monomer that contains reactive hydrogen 100-140 ℃ of reaction, cool off for use;
B, emulsification in advance: the deionized water that in the emulsification still, drops into the ionized water total mass 40%-50% that accounts for; Account for the sodium lauryl sulphate of sodium lauryl sulphate total mass 50%-80% in the emulsifying agent; Account for the isomery alcohol ether TO-8 and whole monomers of isomery alcohol ether TO-8 total mass 60%-90%; Stirring and emulsifying 25-30 minute, form pre-emulsion;
C, polyreaction: in polymeric kettle, drop into the deionized water of the ionized water total mass 30%-50% that accounts for, remaining sodium lauryl sulphate and isomery alcohol ether TO-8 in the emulsifying agent, buffer reagent; Molecular weight regulator stirs and intensification, after temperature reaches 75 ℃; Add the initiator that accounts for initiator total mass 20%-40%, initiator should at first be used deionized water dissolving, forms the initiator solution of 5-10% mass concentration; After 10 minutes, begin to drip respectively pre-emulsion and initiator solution, approximately after 5-20 minute; Polyreaction begins, and can acutely heat up, and keeps emulsion temperature at 85 ℃; The dropping time of pre-emulsion was controlled at 2-4 hour, and initiator solution should be later than pre-emulsion and add in 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 is accomplished, cool to below 45 ℃, to use mass concentration be 20% aqueous sodium hydroxide solution is adjusted to the pH value of emulsion between the 5.5-6.5, filters discharging, promptly obtains having the polymer formaldehyde-trapping agent finished product of retanning filling function.
7. acrylic type polymer formaldehyde-trapping agent of function and preparation method thereof is filled in the retanning that has described in claim 6, it is characterized in that, the solid content of test emulsion sampling is 20%-30%, then is qualified.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110436865.9A CN102558423B (en) | 2011-12-23 | 2011-12-23 | Crylic acid type macromolecule formaldehyde catching agent with retanning filling functions and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110436865.9A CN102558423B (en) | 2011-12-23 | 2011-12-23 | Crylic acid type macromolecule formaldehyde catching agent with retanning filling functions and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102558423A true CN102558423A (en) | 2012-07-11 |
| CN102558423B CN102558423B (en) | 2014-05-21 |
Family
ID=46405146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110436865.9A Active CN102558423B (en) | 2011-12-23 | 2011-12-23 | Crylic acid type macromolecule formaldehyde catching agent with retanning filling functions and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102558423B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104060001A (en) * | 2014-07-10 | 2014-09-24 | 北京泛博科技有限责任公司 | Formaldehyde removal agent and preparation method thereof |
| CN104645800A (en) * | 2013-11-25 | 2015-05-27 | 北京市理化分析测试中心 | Formaldehyde catching agent and preparation method thereof |
| 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 |
| CN110023365A (en) * | 2016-12-05 | 2019-07-16 | 科思创德国股份有限公司 | Acrylate and acrylamide are used to reduce the purposes of the discharge of polyurethane foam |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0676430A2 (en) * | 1994-04-08 | 1995-10-11 | Rohm And Haas Company | Waterborne coating composition |
| CN1129227A (en) * | 1993-08-25 | 1996-08-21 | 罗姆和哈斯公司 | Single package ambient curing polymers |
| EP0897399B1 (en) * | 1996-05-10 | 2002-01-02 | E.I. Du Pont De Nemours And Company | Acrylic polymer compounds |
| CN101367901A (en) * | 2007-08-14 | 2009-02-18 | 陈士安 | High-solid content acrylic acid aqueous composition and method of preparing the same |
-
2011
- 2011-12-23 CN CN201110436865.9A patent/CN102558423B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1129227A (en) * | 1993-08-25 | 1996-08-21 | 罗姆和哈斯公司 | Single package ambient curing polymers |
| EP0676430A2 (en) * | 1994-04-08 | 1995-10-11 | Rohm And Haas Company | Waterborne coating composition |
| EP0897399B1 (en) * | 1996-05-10 | 2002-01-02 | E.I. Du Pont De Nemours And Company | Acrylic polymer compounds |
| CN101367901A (en) * | 2007-08-14 | 2009-02-18 | 陈士安 | High-solid content acrylic acid aqueous composition and method of preparing the same |
Non-Patent Citations (4)
| Title |
|---|
| 余武斌等: "酯交换法合成乙酰乙酸基甲基丙烯酸乙酯新工艺研究", 《浙江工业大学学报》 * |
| 张继德等: "单组分室温交联水性木器涂料的制备", 《湖南工业大学学报》 * |
| 朱杨荣等: "室温自交联杂化硅丙乳液的制备及表征", 《材料科学与工程学报》 * |
| 肖卫东等: "《聚合物材料用化学助剂》", 31 August 2003, 化学工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104645800A (en) * | 2013-11-25 | 2015-05-27 | 北京市理化分析测试中心 | Formaldehyde catching agent and preparation method thereof |
| 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 |
| CN104060001A (en) * | 2014-07-10 | 2014-09-24 | 北京泛博科技有限责任公司 | Formaldehyde removal 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 |
| CN110023365A (en) * | 2016-12-05 | 2019-07-16 | 科思创德国股份有限公司 | Acrylate and acrylamide are used to reduce the purposes of the discharge of 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102558423B (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104449643B (en) | Oil field fracturing fluid heat-resistant polymer thickening agent and preparation method and application | |
| CN101323886B (en) | Preparation of acrylic polymer retanning agent for highly elastic leather retanning | |
| CN102516443B (en) | Method for preparing super absorbent resin | |
| CN102559108B (en) | Preparation method for water-fast starch adhesive with high initial adhesion | |
| CN101280035A (en) | Wet-rub resistant styrene-acrylic emulsion and preparation thereof | |
| CN102558423B (en) | Crylic acid type macromolecule formaldehyde catching agent with retanning filling functions and preparation method thereof | |
| CN103059828B (en) | For viscosifying agent and the synthetic method thereof of aqueous fracturing fluid | |
| CN105566516B (en) | A kind of structure directing type composite initiator system and acrylamide polymer and its preparation method and application | |
| CN104053679A (en) | Dispersion of adsorbing emulsion polymer particles | |
| CN103483499A (en) | Preparation method for carboxylic acrylonitrile butadiene rubber latex for industrial and medical impregnated checking gloves | |
| CN101487207A (en) | Production method of anti-interference paper intensifier | |
| CN103694403B (en) | A kind of preparation method of self-crosslinking polyester film silane coupling agent acrylic ester emulsion | |
| CN102504087B (en) | Preparation method for silicic acrylic ester soap-free emulsion stabilized by protective colloid | |
| CN1146600C (en) | Prepn. of alkali-soluble (methyl) acrylate-based copolymers | |
| CN105566560B (en) | A kind of structure directing type composite initiator system and acrylamide polymer and its preparation method and application | |
| CN102382235B (en) | Acrylic emulsion, preparation method and application thereof | |
| CN103626910A (en) | Solid ethylene-vinyl acetate copolymer and preparation method thereof | |
| CN105968239A (en) | Method for preparing polyacrylate through electrochemical polymerization | |
| CN103224588B (en) | A kind of flocculation agent | |
| CN104761673A (en) | Carbomer and preparation method thereof | |
| CN101338058A (en) | Method for preparing AKD high molecular dispersing agent and use thereof | |
| CN105566515B (en) | A kind of structure directing type composite initiator agent system and acrylamide polymer and its preparation method and application | |
| CN104926974A (en) | Method for preparing styrene-acrylate copolymer | |
| CN102675533A (en) | Ultrasound auxiliary preparation method of hydrophobic association polyacrylamide (HAPAM) | |
| CN102703000A (en) | Modified vinyl acetate multi-copolymer adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |