CN103554349A - Self-crosslinking acrylate emulsion and preparation method thereof - Google Patents
Self-crosslinking acrylate emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses self-crosslinking acrylate emulsion and a preparation method thereof. The self-crosslinking acrylate emulsion is prepared from (methyl) acrylate monomer, a functional monomer, a crosslinking monomer, a crosslinking agent, an emulsifying agent A, an emulsifying agent B, a buffering agent, an initiator, an oxidizer, a reducer and deionized water, wherein the reducer is an FF6M macromolecule polymerization novel reducer produced by a Bruegmann company in Germany, the emulsifying agent A is an emulsifying agent AEROSOL A-501 produced by a Cytel company in America, and the emulsifying agent B is an emulsifying agent AEROSOL MA-80 produced by the Cytel company in America; the preparation method of the self-crosslinking acrylate emulsion comprises pre-emulsification, emulsification and post treatment. A superfine glass fiber separating plate made by adopting the self-crosslinking acrylate emulsion is low in potassium hypermanganate reduzate content, high in liquid absorption speed, high in amount of absorbed liquid and excellent in performance.
Description
Technical field
The present invention relates to a kind of self-crosslinking acrylic ester emulsion and preparation method thereof, relate in particular to a kind of self-crosslinking acrylic ester emulsion of preparing superfine glass fibre partition board and preparation method thereof that is applicable to.
Background technology
Superfine glass fibre partition board is a kind of type material being composited by beta glass fibre mat and glass wool, has good physical strength and anti-vibration performance, and resistivity rate is low, porosity is high, capacity is large, and strong by the store battery startup ability of this dividing plate assembling, work-ing life is also longer.The internal performance of this superfine glass fibre partition board comprises tensile strength, rate of liquid aspiration, potassium permanganate reduzate content and acidproof scale resistance, the principal element that affects superfine glass fibre partition board performance is the binding agent using in its preparation process, and self-crosslinking acrylic ester emulsion is current the most frequently used a kind of binding agent.
Self-crosslinking acrylic ester emulsion is normally formed through radical polymerization by (methyl) vinylformic acid (ester) monomer, cross-linking monomer, emulsifying agent, buffer reagent, initiator and deionized water etc.Wherein cross-linking monomer is all to adopt N hydroxymethyl acrylamide mostly, but this cross-linking monomer can produce formaldehyde in cross-linking process, thereby makes the acrylic ester emulsion making have larger harm to human body.
Chinese patent literature CN102358769A discloses a kind of normal temperature self-crosslinking acrylic emulsion and preparation method thereof, and this emulsion is formed by free radical polymerization by deionized water, emulsifying agent RN-30, butyl acrylate, methyl methacrylate, Hydroxyethyl acrylate, vinylformic acid, vinyltrimethoxy silane, sodium bicarbonate, ammonium persulphate, diacetone-acryloamide(DAA), adipic dihydrazide, oxygenant tertbutyl peroxide, reductive agent rongalite and ammoniacal liquor.The deficiency of the document is: the wetting ability of (1) emulsifying agent RN-30 own is just poor, and when pre-emulsification and emulsification, all adopt this emulsifying agent, make so the emulsion wettability that finally obtains poor, the superfine glass fibre partition board rate of liquid aspiration that adopts the poor emulsion of this wettability to prepare is slower, and liquid absorption is less.(2) post-processing stages adopts oxygenant tertbutyl peroxide and reductive agent rongalite to remove residual monomer, and on the one hand, this mode removal efficiency is low, and poor effect still has the residual monomer of larger content; On the other hand, adopt rongalite also easily to produce formaldehyde, thus harmful.The most important thing is, the unsaturated double-bond in residual monomer and formaldehyde all have certain reductibility, thereby easily react with potassium permanganate, finally cause prepared superfine glass fibre partition board potassium permanganate reduzate content higher, have affected product performance.Therefore, this self-crosslinking acrylic ester emulsion is not suitable for and prepares superfine glass fibre partition board.
Summary of the invention
The object of the invention is to address the above problem, a kind of self-crosslinking acrylic ester emulsion that is applicable to the superfine glass fibre partition board of processability excellence is provided.
Another object of the present invention is to provide the preparation method of above-mentioned self-crosslinking acrylic ester emulsion.
The technical scheme that realizes one of the object of the invention is: a kind of self-crosslinking acrylic ester emulsion, by the component of following weight per-cent, made: (methyl) acrylate monomer of 40%～50%; 0.3%～1.5% function monomer; 1.0%～3.0% cross-linking monomer; 0.5%～1.5% linking agent; 0.5%～1.5% emulsifying agent A; 0.1%～0.2% emulsifying agent B; 0.1%～0.3% buffer reagent; 0.15%～0.4% initiator; 0.05%～0.2% oxygenant; 0.05%～0.2% reductive agent; 45%～55% deionized water; Described reductive agent is the FF6M high molecular polymerization novel reducer that German Brueggemann company produces.
Described emulsifying agent A is the emulsifying agent AEROSOL A-501 that U.S. Qing Te company produces; Described emulsifying agent B is the emulsifying agent AEROSOL MA-80 that U.S. Qing Te company produces.
Described (methyl) acrylate monomer is a kind of in ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate or two kinds or three kinds; Described function monomer is a kind of in vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid or two kinds or three kinds.
Described cross-linking monomer is diacetone-acryloamide(DAA); Described linking agent is adipic dihydrazide.
Described buffer reagent is sodium bicarbonate; Described initiator is ammonium persulphate; Described oxygenant is tertbutyl peroxide.
The technical scheme that realizes another object of the present invention is: the preparation method of above-mentioned self-crosslinking acrylic ester emulsion, has following steps:
1. pre-emulsification: to 20%～30% deionized water and the emulsifying agent A that add the ionized water gross weight that accounts in pre-emulsification still; After stirring, add successively function monomer, cross-linking monomer and (methyl) acrylate monomer, continue to stir and carry out pre-emulsification, obtain pre-emulsion stand-by.
2. emulsification: first, 45%～55% deionized water, emulsifying agent B and buffer reagent to adding the ionized water gross weight that accounts in reactor, stir and be warming up to 75 ℃～80 ℃, adds 5%～15% the pre-emulsion that accounts for pre-emulsion gross weight that 1. step make; Then, add pre-cast initiation solution, now temperature rises gradually; Described pre-cast initiation solution is comprised of 70%～80% initiator and the deionized water that account for initiator gross weight; Then, reach 84 ℃～86 ℃ and while no longer rising to temperature, slowly drip the residue pre-emulsion of step in 1., drip residue initiation solution simultaneously; Drip off and be warming up to 88 ℃～90 ℃ insulation 50min～70min; Described residue initiation solution is comprised of 20%～30% initiator and the deionized water that account for initiator gross weight.
3. aftertreatment: after insulation finishes, be first cooled to 55 ℃～65 ℃, add successively the oxidizing agent solution being formed by oxygenant and deionized water and the reductant solution being formed by reductive agent and deionized water, add insulation 0.5h～1.0h; Be cooled to again envrionment temperature, add the cross-linking agent solution being formed by linking agent and deionized water, stir, filter discharging, obtain self-crosslinking acrylic ester emulsion.
The positively effect that the present invention has: (1) self-crosslinking acrylic ester emulsion of the present invention adopts FF6M high molecular polymerization novel reducer to replace rongalite, so not only greatly improved the efficiency of removing residual monomer, obviously reduced the residual quantity of monomer, and avoided the generation of formaldehyde, make the superfine glass fibre partition board being made by this emulsion there is lower potassium permanganate reduzate content, excellent performance.(2) self-crosslinking acrylic ester emulsion of the present invention adopts emulsifying agent AEROSOL A-501 in the pre-emulsification stage, at emulsifying stage, adopt AEROSOL MA-80, emulsifying property and wettability have been taken into account like this, especially emulsifying agent AEROSOL MA-80 has the few and unsettled characteristic of foam, make the emulsion finally obtaining there is splendid wettability, finally make that the superfine glass fibre partition board rate of liquid aspiration that made by this emulsion is very fast, liquid absorption is higher.(3) self-crosslinking acrylic ester emulsion preparation manipulation of the present invention is simple, and without special equipment, and reaction is easy to control, applicable suitability for industrialized production.(4) superfine glass fibre partition board of being made by self-crosslinking acrylic ester emulsion of the present invention also has the advantages such as aperture is little, surface-area is large, porosity is high, chemical purity is high, detrimental impurity is few, resistivity is low, and has extraordinary acid resistance and oxidation-resistance.
Embodiment
(embodiment 1)
The preparation method of the self-crosslinking acrylic ester emulsion of the present embodiment, has following steps:
1. pre-emulsification:
(0～40 ℃ at ambient temperature, lower same), to what add that the deionized water of 60kg and emulsifying agent A(the present embodiment of 5kg adopt in the pre-emulsification still with agitator, reflux exchanger and thermometer, be the AEROSOL A-501 that U.S. Qing Te company produces), with the speed of 150 revs/min, stir 15 minutes.
After stirring, add successively the methacrylic acid of 3kg, the methyl methacrylate of the diacetone-acryloamide(DAA) of 7kg, 80kg and the ethyl propenoate of 130kg, add, first rotating speed being risen to 450 revs/min stirs 30 minutes, rotating speed is down to 100 revs/min again and stirs 10 minutes, the pre-emulsion that obtains 285kg is stand-by.
2. emulsification:
First, at ambient temperature, to adding the deionized water of 140kg in the reactor with agitator, reflux exchanger and thermometer, emulsifying agent B(the present embodiment of 0.5kg adopts is the AEROSOL MA-80 that U.S. Qing Te company produces) and the buffer reagent sodium bicarbonate of 0.5kg, stirring is warming up to 78 ℃ ± 1 ℃, adds pre-emulsion that 1. 28.5kg step make as seed liquor.
Then, add pre-cast initiation solution (being comprised of the ammonium persulphate of 0.7kg and the deionized water of 21kg), now temperature rises gradually.
Then, reach 85 ℃ ± 1 ℃ and while no longer rising (approximately 20 minutes) to temperature, slowly drip the residue pre-emulsion of step in 1., drip residue initiation solution (being formed by the ammonium persulphate of 0.2kg and the deionized water of 8kg) simultaneously.
Whole time for adding is controlled at 3h～4h, and temperature is controlled at 85 ℃ ± 1 ℃.
Drip off and be warming up to 89 ℃ ± 1 ℃ insulation 1h.
3. aftertreatment:
After insulation finishes, be cooled to 60 ℃ ± 1 ℃, first add oxidizing agent solution (being formed by the tertbutyl peroxide of 0.3kg and the deionized water of 5kg), stir after 5min, add again reductant solution (the FF6M high molecular polymerization novel reducer of being produced by the German Brueggemann company of 0.3kg and the deionized water of 10kg form), then be incubated after 40min, be cooled to 35 ℃, add cross-linking agent solution (being formed by the adipic dihydrazide of 3.5kg and the deionized water of 15kg), add and continue to stir 10min, filter discharging, obtaining solid content is 45wt%, viscosity is 80mPas, milky self-crosslinking acrylic ester emulsion.
(embodiment 2～embodiment 3)
Each embodiment is substantially the same manner as Example 1, and difference is in Table 1.
Table 1
。
(application examples)
The self-crosslinking acrylic ester emulsion that embodiment 1 to embodiment 3 is made is applied in the moulding process of superfine glass fibre partition board and makes superfine glass fibre partition board, product performance are according to JB/T7603.1-2008 < < lead acid cell superfine glass fibre partition board > > standard test, and each performance index are in Table 2.
Table 2
。
(contrast application examples)
The emulsion applications that Chinese patent literature CN102358769A example 3-1 is made makes superfine glass fibre partition board in the moulding process of superfine glass fibre partition board, product performance are according to JB/T7603.1-2008 < < lead acid cell superfine glass fibre partition board > > standard test, and each performance index are in Table 3.
Table 3
| Project | CN102358769A |
| Tensile strength (felt plate thickness 1～1.5mm) | 0.9kN/m |
| Resistance | 0.00060Ω/dm 2 |
| Wettability | 65s |
| Potassium permanganate reduzate content | 18mL/g |
| Pickling is weightless | 1.5% |
| Iron level | ≤0.005% |
| Cl content | ≤0.003% |
| Foaminess | Bubble covers sulphuric acid soln surface completely, and is difficult for breaking |
。
Claims (10)
1. a self-crosslinking acrylic ester emulsion, is characterized in that being made by the component of following weight per-cent:
(methyl) acrylate monomer of 40%～50%;
0.3%～1.5% function monomer;
1.0%～3.0% cross-linking monomer;
0.5%～1.5% linking agent;
0.5%～1.5% emulsifying agent A;
0.1%～0.2% emulsifying agent B;
0.1%～0.3% buffer reagent;
0.15%～0.4% initiator;
0.05%～0.2% oxygenant;
0.05%～0.2% reductive agent;
45%～55% deionized water;
Described reductive agent is the FF6M high molecular polymerization novel reducer that German Brueggemann company produces.
2. self-crosslinking acrylic ester emulsion according to claim 1, is characterized in that: described emulsifying agent A is the emulsifying agent AEROSOL A-501 that U.S. Qing Te company produces; Described emulsifying agent B is the emulsifying agent AEROSOL MA-80 that U.S. Qing Te company produces.
3. self-crosslinking acrylic ester emulsion according to claim 1 and 2, is characterized in that: described (methyl) acrylate monomer is a kind of in ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate or two kinds or three kinds; Described function monomer is a kind of in vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid or two kinds or three kinds.
4. self-crosslinking acrylic ester emulsion according to claim 1 and 2, is characterized in that: described cross-linking monomer is diacetone-acryloamide(DAA); Described linking agent is adipic dihydrazide.
5. self-crosslinking acrylic ester emulsion according to claim 1 and 2, is characterized in that: described buffer reagent is sodium bicarbonate; Described initiator is ammonium persulphate; Described oxygenant is tertbutyl peroxide.
6. the preparation method of self-crosslinking acrylic ester emulsion claimed in claim 1, is characterized in that having following steps:
1. pre-emulsification:
To 20%～30% deionized water and the emulsifying agent A that add the ionized water gross weight that accounts in pre-emulsification still; After stirring, add successively function monomer, cross-linking monomer and (methyl) acrylate monomer, continue to stir and carry out pre-emulsification, obtain pre-emulsion stand-by;
2. emulsification:
First, 45%～55% deionized water, emulsifying agent B and buffer reagent to adding the ionized water gross weight that accounts in reactor, stir and be warming up to 75 ℃～80 ℃, adds 5%～15% the pre-emulsion that accounts for pre-emulsion gross weight that 1. step make;
Then, add pre-cast initiation solution, now temperature rises gradually; Described pre-cast initiation solution is comprised of 70%～80% initiator and the deionized water that account for initiator gross weight;
Then, reach 84 ℃～86 ℃ and while no longer rising to temperature, slowly drip the residue pre-emulsion of step in 1., drip residue initiation solution simultaneously; Drip off and be warming up to 88 ℃～90 ℃ insulation 50min～70min; Described residue initiation solution is comprised of 20%～30% initiator and the deionized water that account for initiator gross weight;
3. aftertreatment:
After insulation finishes, be first cooled to 55 ℃～65 ℃, add successively the oxidizing agent solution being formed by oxygenant and deionized water and the reductant solution being formed by reductive agent and deionized water, add insulation 0.5h～1.0h; Be cooled to again envrionment temperature, add the cross-linking agent solution being formed by linking agent and deionized water, stir, filter discharging, obtain self-crosslinking acrylic ester emulsion.
7. the preparation method of self-crosslinking acrylic ester emulsion according to claim 6, is characterized in that: described emulsifying agent A is the emulsifying agent AEROSOL A-501 that U.S. Qing Te company produces; Described emulsifying agent B is the emulsifying agent AEROSOL MA-80 that U.S. Qing Te company produces.
8. according to the preparation method of the self-crosslinking acrylic ester emulsion described in claim 6 or 7, it is characterized in that: described (methyl) acrylate monomer is a kind of in ethyl propenoate, butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate or two kinds or three kinds; Described function monomer is a kind of in vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid or two kinds or three kinds.
9. according to the preparation method of the self-crosslinking acrylic ester emulsion described in claim 6 or 7, it is characterized in that: described cross-linking monomer is diacetone-acryloamide(DAA); Described linking agent is adipic dihydrazide.
10. according to the preparation method of the self-crosslinking acrylic ester emulsion described in claim 6 or 7, it is characterized in that: described buffer reagent is sodium bicarbonate; Described initiator is ammonium persulphate; Described oxygenant is tertbutyl peroxide.
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| CN104059192A (en) * | 2014-07-04 | 2014-09-24 | 青岛科技大学 | Non-blending type ACM water swelling rubber and mass polymeriatio preparing method thereof |
| CN104910319A (en) * | 2015-06-04 | 2015-09-16 | 东莞长联新材料科技股份有限公司 | Polyacrylate emulsion capable of postponing dye transfer and preparation method thereof |
| CN104277188B (en) * | 2014-09-23 | 2017-02-15 | 合肥乐凯科技产业有限公司 | Self-crosslinking acrylate emulsion as well as preparation method and application thereof |
| CN109233530A (en) * | 2018-08-28 | 2019-01-18 | 常州赛维化工有限公司 | Super abrasive water-based road guide line coating and preparation method thereof |
| CN110685155A (en) * | 2019-10-11 | 2020-01-14 | 西安工程大学 | Quick-drying type crosslinked polyacrylic acid textile size and preparation method thereof |
| CN110903729A (en) * | 2019-12-13 | 2020-03-24 | 湖北科迪雅科技有限公司 | Energy storage type luminous paint for environment-friendly plastic base and preparation method thereof |
| CN111574660A (en) * | 2020-05-26 | 2020-08-25 | 东联北方科技(北京)有限公司 | Preparation method of crosslinked acrylate emulsion and product prepared by preparation method |
| CN112201880A (en) * | 2020-09-28 | 2021-01-08 | 消之源科技技术有限公司 | Preparation method of automatic intelligent cooling partition plate for new energy lithium battery |
| CN112724831A (en) * | 2021-04-01 | 2021-04-30 | 佛山市昭景环保科技有限公司 | Water-based treating agent for printing burst-style synthetic leather and preparation method thereof |
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| CN104277188B (en) * | 2014-09-23 | 2017-02-15 | 合肥乐凯科技产业有限公司 | Self-crosslinking acrylate emulsion as well as preparation method and application thereof |
| CN104910319A (en) * | 2015-06-04 | 2015-09-16 | 东莞长联新材料科技股份有限公司 | Polyacrylate emulsion capable of postponing dye transfer and preparation method thereof |
| CN109233530A (en) * | 2018-08-28 | 2019-01-18 | 常州赛维化工有限公司 | Super abrasive water-based road guide line coating and preparation method thereof |
| CN110685155A (en) * | 2019-10-11 | 2020-01-14 | 西安工程大学 | Quick-drying type crosslinked polyacrylic acid textile size and preparation method thereof |
| CN110903729A (en) * | 2019-12-13 | 2020-03-24 | 湖北科迪雅科技有限公司 | Energy storage type luminous paint for environment-friendly plastic base and preparation method thereof |
| CN111574660A (en) * | 2020-05-26 | 2020-08-25 | 东联北方科技(北京)有限公司 | Preparation method of crosslinked acrylate emulsion and product prepared by preparation method |
| CN112201880A (en) * | 2020-09-28 | 2021-01-08 | 消之源科技技术有限公司 | Preparation method of automatic intelligent cooling partition plate for new energy lithium battery |
| CN112724831A (en) * | 2021-04-01 | 2021-04-30 | 佛山市昭景环保科技有限公司 | Water-based treating agent for printing burst-style synthetic leather and preparation method thereof |
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| CN114656904A (en) * | 2022-04-12 | 2022-06-24 | 珠海冠宇电池股份有限公司 | Binder and battery comprising same |
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Effective date of registration: 20160831 Address after: 213022 Jiangsu city in Changzhou Province town of Hua Lu Wei Chunjiang New District No. 2 Patentee after: Changzhou Hickory Chemistry Co., Ltd. Address before: 213127 No. 501 ERON North Road, Xinbei District, Jiangsu, Changzhou Patentee before: Changzhou Tianma Group Co., Ltd. (former building material 253 factory) |
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Effective date of registration: 20201215 Address after: 309 Huanghai Road, Xinbei District, Changzhou City, Jiangsu Province Patentee after: CHANGZHOU TIANMA GROUP Co.,Ltd. (BUILDING TWO FIVE THREE FACTORY) Address before: No.2, Weihua Road, Chunjiang Town, Xinbei District, Changzhou City, Jiangsu Province Patentee before: CHANGZHOU HICKORY CHEMICAL Co.,Ltd. |