CN1410462A - Preparation of environmental protection type low temperature water acrylate copoly latex and its application - Google Patents
Preparation of environmental protection type low temperature water acrylate copoly latex and its application Download PDFInfo
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- CN1410462A CN1410462A CN 02145356 CN02145356A CN1410462A CN 1410462 A CN1410462 A CN 1410462A CN 02145356 CN02145356 CN 02145356 CN 02145356 A CN02145356 A CN 02145356A CN 1410462 A CN1410462 A CN 1410462A
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Abstract
An environment protection type low-temp. water acrylate copolylatex is prepared through copolymerization between multi-element monomer and cross-linking component containing 2 or more double-bonds. It has 20-40% of solid content and -30- +25 deg.C of vitrification temp., and can be used as low-temp. adhesive or water paint.
Description
Technical field:
The invention belongs to the light industry chemical technology field.Be specifically related to a kind of environment-friendly type low temperature water-based acrylic ester copolymer latex preparation and application thereof.
Background technology:
Have good fast light, ageing-resistant, oil resistant and acid-proof alkaline by the made glued membrane of polyacrylic ester latex, and it there is good adhesive performance to fiber, leather, paper etc.Therefore this latex is widely used in aspects such as coating, fabric and process hides.Aspect fabric applications, the main tackiness agent of using as dyeing and printing adhesive agent, textile coating agent, thickening material and anti-pilling agent, bonded fabric product etc.
Non-crosslinked, external crosslinking and self-crosslinking three phases have been passed through in the development of water-and acrylate copolymer latex, but these crosslinked conditions all compare harsh, need higher temperature (about 160 ℃) and lower pH value, both wasted resource, increased damage again, and also discharged harmful formaldehyde material in the application process the processing base material.Implement water-and acrylate copolymer latex crosslinked at low temperature, someone adopts the method for extra catalyst: the mixture (amount than be 1: 1) that uses Magnesium dichloride hexahydrate and citric acid, make the bi-component low-temperature cure adhesive of catalyzer as Azcat A, but rise when main weak point is to use and to be equipped with catalyzer, cumbersome, and configuration product stability is not good, and residual slurry can't reuse etc.Another approach is to take the radiation-induced crosslinking technology, but this need add special equipment, and cost is than higher.The somebody replace formaldehyde emission matter N hydroxymethyl acrylamide, but the problem that this technology is brought is to have added the AOX pollution to environment by introducing the activity epoxide group with epichlorohydrin reaction.
Summary of the invention:
The technical problem to be solved in the present invention is to overcome above-mentioned weak point, and macromole that designs a kind of special construction and preparation method thereof makes the latex main body of formation have the reticulated structure of certain precrosslink degree but not linear macromolecule.
The invention provides a kind of preparation method of environment-friendly type low temperature water-based acrylic ester copolymer latex, this method is to participate in copolymerization by add the bridging property component contain two keys more than two and two in polynary monomer, in polymerization process in macromole to a certain degree crosslinked of introduction.
Embodiment:
(1) raw material:
(a) monomer: butyl acrylate (BA), 2 ethyl hexyl acrylate (2-EHA), vinylbenzene (St), methacrylic acid (MAA), N hydroxymethyl acrylamide (NMA), comonomer A, methyl methacrylate (MMA) [all from the auxiliary reagent factory, Shanghai].
(b) emulsifying agent: paregal O, OS, sodium lauryl sulphate (auxiliary reagent factory, Shanghai); TX-30 (chemical plant, Hai'an, Jiangsu)
(c) initiator: ammonium persulphate (auxiliary reagent factory, Shanghai)
(2) schedule of operation:
The there-necked flask that agitator, reflux condensing tube, dropping funnel are housed is placed on the temperature controlled water bath, add emulsifying agent and distilled water, stir, be warming up to 78-80 ℃, add initiator, after stirring for some time, drip monomer, the control rate of addition continues to append the residue initiator after dropwising.After insulation for some time, be warming up to again about 90 ℃, insulation, cooling promptly gets product.
The latex feature that makes with the inventive method is as follows:
The solid content of this latex is between 20% ∽ 40%, and second-order transition temperature is-30 ℃ of ∽+25 ℃, (components by weight percent) composed as follows:
30 ∽, 65% butyl acrylates (BA)
5 ∽, 30% 2-EHAs (2-EHA)
5 ∽, 30% vinylbenzene (St)
1 ∽, 10% multi-functional comonomer A
2 ∽, 7% methacrylic acids (MAA)
0 ∽, 3% N hydroxymethyl acrylamide (NMA)
4 ∽, 12% methyl methacrylates (MMA)
The bridging property component is the multi-functional comonomer that contains two keys more than two and two in this latex, and its consumption has determined the character of copolymer latex.
The latex that makes with the inventive method has following advantage and energy widespread use:
1. this latex serves many purposes, and can be used as the low formaldehyde binder of low temperature, low temperature formaldehyde binder, low temperature coating-forming agent, anti-pilling agent etc.
2. when this latex was used, 100 ℃ of oven dry got final product, and generally need not bake, just the performance that can obtain.
3. this latex need not use the melmac outside cross-linking agent, has stopped harmful formaldehyde problem, and does not have AOX and pollute.For the low formaldehyde type of low temperature, less because of the N hydroxymethyl acrylamide consumption, burst size of methanal is lower than 30ppm after measured, meets the Eco standard.
4. this latex is as low-temperature-based adhesive, and soft, dried fastness to wet rubbing is respectively 4 grades of 4 and 3 ∽.As the low temperature coating-forming agent, after the oven dry of coating one deck, hydraulic pressure reaches more than the 1000mm water column, be coated with two-layer oven dry after, hydraulic pressure reaches the 2000mm water column.Film-forming properties latex is as the worsted anti-pilling agent, and fastness reaches more than 4 grades.
Embodiment 1:
A. copolymer latex as the preparation of the low formaldehyde binder of low temperature (solid content: 40%) latex is formed:
The monomeric species consumption
Butyl acrylate 30%
2 ethyl hexyl acrylate 30%
Vinylbenzene 30%
Methacrylic acid 2%
N hydroxymethyl acrylamide 3%
Methyl methacrylate 4%
Comonomer A 1% preparation method:
Paregal O and TX-30 with 0.5 ∽ 2.0%, 0.2 adding after with dissolved in distilled water, the OS of ∽ 1.5g and sodium lauryl sulphate be equipped with in the there-necked flask of agitator, reflux condensing tube, dropping funnel, stir, be warming up to 78-80 ℃, the ammonium persulfate aqueous solution that adds 0.2 ∽ 0.8% after stirring for some time, drips the aqueous solution of oiliness monomer and NMA respectively, the control rate of addition, 2 ∽ dripped in 3 hours.After continue to append the residue initiator (0.02 ∽ 0.08%), be incubated 15 ∽ 30min, be warming up to again about 90 ℃, the insulation, the cooling, promptly get product.B. the application mill base of the low formaldehyde binder of low temperature is formed:
Tackiness agent (40% solid content) 20%
Coating 5%
Thickening material 2%
Water is to total amount 100%
Ammoniacal liquor pH transfers to 7 ∽ 8
Technology 1: PLATE SCREAM PRINTING (100 order): → oven dry (100 ℃) → finished product 1
Technology 2: PLATE SCREAM PRINTING (100 order): → oven dry (80 ℃) → finished product 2
The result:
Dry fastness wet friction jail feel formaldehyde discharges
Tolerance
4 grades of 3-4 level softness＜30ppm of finished product 1 (technology 1)
4 grades of 3 grades of softness＜30ppm of finished product 2 (technology 2)
Embodiment 2:
A. copolymer latex as the preparation of low temperature formaldehyde binder (solid content: 40%) latex is formed:
The monomeric species consumption
Butyl acrylate 65%
2 ethyl hexyl acrylate 5%
Vinylbenzene 5%
Methacrylic acid 7%
Methyl methacrylate 12%
Comonomer A 6% preparation method:
Paregal O and TX-30 with 0.5 ∽ 2%, 0.2 adding after with dissolved in distilled water, the OS of ∽ 1.5% and sodium lauryl sulphate be equipped with in the there-necked flask of agitator, reflux condensing tube, dropping funnel, stir, be warming up to 78-80 ℃, the ammonium persulfate aqueous solution that adds 0.2 ∽ 0.8% after stirring for some time, drips monomer, the control rate of addition, 2 ∽ dripped in 3 hours.After continue to append the residue initiator (0.01 ∽ 0.08%), be incubated 15 ∽ 30min, be warming up to again about 90 ℃, the insulation, the cooling, promptly get product.B. the application mill base of low temperature formaldehyde binder is formed:
Tackiness agent (40% solid content) 20%
Coating 5%
Thickening material 2%
Water is to total amount 100%
Ammoniacal liquor pH transfers to 7 ∽ 8
Technology 3: PLATE SCREAM PRINTING (100 order): → oven dry (100 ℃) → finished product 3
Technology 4: PLATE SCREAM PRINTING (100 order): → oven dry (80 ℃) → finished product 4 results:
Wet friction jail, metal to-metal contact jail feel
The degree degree
4 grades of 3-4 level softnesses of finished product 3 (technology 3)
3 grades of softnesses of finished product 4 (technology 4) 3-4 level
Embodiment 3:
A. copolymer latex is formed as the preparation latex of low temperature coating-forming agent:
The monomeric species consumption
Butyl acrylate 45%
2 ethyl hexyl acrylate 18%
Vinylbenzene 17%
Methacrylic acid 4.5%
N hydroxymethyl acrylamide 1.5%
Methyl methacrylate 4%
Comonomer A 10% preparation method:
Peregal 0 and TX-30 with 0.5 ∽ 2%, 0.2 adding after with dissolved in distilled water, the OS of ∽ 1.5% and sodium lauryl sulphate be equipped with in the there-necked flask of agitator, reflux condensing tube, dropping funnel, stir, be warming up to 78-80 ℃, the ammonium persulfate aqueous solution that adds 0.2 ∽ 1% after stirring for some time, drips the aqueous solution of oiliness monomer and NMA respectively, the control rate of addition, 2 ∽ dripped in 3 hours.After continue to append the residue initiator (0.01 ∽ 0.1%), be incubated 15 ∽ 30min, be warming up to again about 90 ℃, the insulation, the cooling, promptly get product.B. the application of low temperature coating-forming agent
Coating adhesive is formed: coating-forming agent+thickening material+ammoniacal liquor modulation pH6 ∽ 7
Technology: scraper coating → oven dry (80 ℃) → finished product
The result:
Hydraulic pressure (mm water column)
Coating one deck＞1000
Be coated with two-layer 2000
Claims (6)
1. environment-friendly type low temperature water-based acrylic ester copolymer latex preparation method, it is characterized in that this method is that the there-necked flask that will agitator, reflux condensing tube, dropping funnel be housed places on the temperature controlled water bath, add emulsifying agent and distilled water, stir, be warming up to 78-80 ℃, add initiator, after stirring for some time, dropping contains the mix monomer of multi-functional comonomer A, and the control rate of addition continues to append the residue initiator after dropwising.After insulation for some time, be warming up to again about 90 ℃, insulation, cooling promptly gets product.
2. a kind of environment-friendly type low temperature water-based acrylic ester copolymer latex preparation method according to claim 1 is characterized in that described monomer is butyl acrylate, 2 ethyl hexyl acrylate, vinylbenzene, methacrylic acid, N hydroxymethyl acrylamide, methyl methacrylate and multi-functional monomer A.
3. multi-functional comonomer A according to claim 1 is characterized in that molecule is made up of the vinyl derivative that contains two keys more than two and two.
4. a kind of environment-friendly type low temperature water-based acrylic ester copolymer latex preparation method according to claim 1 is characterized in that described emulsifying agent is paregal O, OS, sodium lauryl sulphate and TX-30; Initiator is an ammonium persulphate.
5. a kind of environment-friendly type low temperature water-based acrylic ester copolymer latex preparation method according to claim 1, the solid content that it is characterized in that the latex that makes with this method is between 20% ∽ 40%, second-order transition temperature is-30 ℃ of ∽+25 ℃, and its composition is by weight percentage:
30 ∽, 65% butyl acrylates (BA)
5 ∽, 30% 2-EHAs (2-EHA)
5 ∽, 30% vinylbenzene (St)
1 ∽, 10% multi-functional comonomer A
2 ∽, 7% methacrylic acids (MAA)
0 ∽, 3% N hydroxymethyl acrylamide (NMA)
4 ∽, 12% methyl methacrylates (MMA)
One kind according to claim 1 a kind of environment-friendly type low temperature water-based acrylic ester copolymer latex of making of method as the application in the low formaldehyde binder of low temperature, low temperature formaldehyde binder, low temperature coating-forming agent and the anti-pilling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02145356 CN1218976C (en) | 2002-11-25 | 2002-11-25 | Preparation of environmental protection type low temperature water acrylate copoly latex and its application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02145356 CN1218976C (en) | 2002-11-25 | 2002-11-25 | Preparation of environmental protection type low temperature water acrylate copoly latex and its application |
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| Publication Number | Publication Date |
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| CN1410462A true CN1410462A (en) | 2003-04-16 |
| CN1218976C CN1218976C (en) | 2005-09-14 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735541A (en) * | 2009-11-10 | 2010-06-16 | 上海漠王复合材料科技有限公司 | Environmental-friendly type emulsion for heat insulating material and preparation method thereof |
| CN102433747A (en) * | 2011-09-19 | 2012-05-02 | 上海大学 | Method for reducing pilling performance of acrylic fabric with active acrylate polymer |
| CN108231301A (en) * | 2017-12-30 | 2018-06-29 | 江苏华友装饰工程有限公司 | A kind of preparation method of high temperature resistance high heat conduction mica tape |
| CN108440745A (en) * | 2018-02-10 | 2018-08-24 | 谢新昇 | A kind of preparation method of weather-proof high temperature resistance polyester resin |
| CN108949071A (en) * | 2018-07-11 | 2018-12-07 | 翟琳 | A kind of preparation method of low viscous lower shrinkage impregnant |
-
2002
- 2002-11-25 CN CN 02145356 patent/CN1218976C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735541A (en) * | 2009-11-10 | 2010-06-16 | 上海漠王复合材料科技有限公司 | Environmental-friendly type emulsion for heat insulating material and preparation method thereof |
| CN102433747A (en) * | 2011-09-19 | 2012-05-02 | 上海大学 | Method for reducing pilling performance of acrylic fabric with active acrylate polymer |
| CN108231301A (en) * | 2017-12-30 | 2018-06-29 | 江苏华友装饰工程有限公司 | A kind of preparation method of high temperature resistance high heat conduction mica tape |
| CN108440745A (en) * | 2018-02-10 | 2018-08-24 | 谢新昇 | A kind of preparation method of weather-proof high temperature resistance polyester resin |
| CN108949071A (en) * | 2018-07-11 | 2018-12-07 | 翟琳 | A kind of preparation method of low viscous lower shrinkage impregnant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1218976C (en) | 2005-09-14 |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Changzhou Golden Spring Textile Co., Ltd. Assignor: Donghua University Contract fulfillment period: 2009.8.8 to 2014.8.7 contract change Contract record no.: 2009320001566 Denomination of invention: Preparation of environmental protection type low temperature water acrylate copoly latex and its application Granted publication date: 20050914 License type: Exclusive license Record date: 2009.8.18 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.8.8 TO 2014.8.7; CHANGE OF CONTRACT Name of requester: CHANGZHOU GOLDEN SPRING FABRICS CO., LTD. Effective date: 20090818 |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050914 Termination date: 20141125 |
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