CN1847350A - Pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material and its prepn process - Google Patents
Pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material and its prepn process Download PDFInfo
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- CN1847350A CN1847350A CN 200510064435 CN200510064435A CN1847350A CN 1847350 A CN1847350 A CN 1847350A CN 200510064435 CN200510064435 CN 200510064435 CN 200510064435 A CN200510064435 A CN 200510064435A CN 1847350 A CN1847350 A CN 1847350A
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Abstract
The present invention discloses pressure-sensitive polyactylate emulsion glue/clay intercalation composite material and its preparation process. The pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material has the components including acrylate monomer 100 weight portions, clay 1-5 weight portions, dispersing medium 125-135 weight portions, initiator 0.1-1 weight portion and emulsifier 1-5 weight portions. The present invention adopts water as the dispersing medium and has the advantages of environment friendship, low cost, high safety, etc. The preparation process is efficient and short in period, and the produced pressure-sensitive polyactylate emulsion glue/clay intercalation composite material possesses excellent performance.
Description
Technical field
The present invention relates to a kind of pressure-sensitive polyacrylate emulsion glue, particularly relate to pressure-sensitive polyacrylate emulsion glue matrix material of a kind of clay filled reinforcement and preparation method thereof.
Background technology
Pressure sensitive adhesive be meant only need give certain pressure just can be wetting by maxxaedium, and produce a class tackiness agent of practical bonding strength.Wherein pressure-sensitive polyacrylate emulsion glue is because easily manufactured, non-environmental-pollution, appearance colorless is transparent and advantage development such as good weatherability is very rapid.The year of China's polyacrylate pressure-sensitive emulsion volume of production and marketing surpassed 200,000 tons, the emulsion pressure-sensitive goods reached more than 5,000,000,000 square meters in 2004.Yet pressure-sensitive polyacrylate emulsion glue also exists some shortcomings, and its pressure-sensitive adhesive cohesive strength is poor, and heat-resisting water resistance difference etc. have limited the application of emulsion pressure-sensitive on some expensive goods to a great extent.Simultaneously because the continuous rise of acrylate monomer price in recent years, the market competition of pressure-sensitive polyacrylate emulsion glue is very fierce, and the profit of producing and managing is very thin.These factors have all limited further developing of pressure-sensitive polyacrylate emulsion glue greatly.The pressure-sensitive polyacrylate emulsion glue utmost point of new high-performance, low price is waited to research and develop.
Summary of the invention
The purpose of this invention is to provide good pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material of strong, the heat-resisting water resistance of a kind of adhesiveproperties and preparation method thereof.
Pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material provided by the present invention comprises following components by part by weight:
Acrylate monomer 100,
Clay 1～5,
Dispersion medium 125-135,
Initiator 0.1～1,
Emulsifying agent 1～5.
The acrylate monomer that is suitable among the present invention includes the soft monomer of low Tg, as: ethyl propenoate, butyl acrylate, ethyl acrylate; The hard monomer of high glass transition temperature is as methyl methacrylate; And the polar monomer that contains carboxyl, hydroxyl isopolarity group, as: vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate etc., these acrylate monomers can directly adopt industrial raw material.
The used clay of the present invention is the nonmetal stratiform silicate minerals of a class, main mineralogical composition is the lamellar aluminosilicate that contains 80% above polynite, its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two.Electronegative in the clay seam, interlayer is the sodium ion exchangeable cation, and ion-exchange total volume (CEC) is 80～120meq/100g, and thickness of clay soil is 0.9～1.1nm, and interfloor distance is 0.96～1.54nm.This montmorillonite clay preferably is crushed to suitable particle diameter, and available ball mill, vibration mill, jet mill etc. are broken into desirable particle size to clay powder, and general particle diameter should be at 30～50 microns.
The dispersion medium that is adopted is a water; Initiator is a thermolysis type initiator, is preferably ammonium persulphate or Potassium Persulphate; Emulsifying agent is selected from one or more in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate and the Nonyl pheno base ether.
The preparation method of this pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material comprises the steps:
1) the 1-5 parts by weight of clay is scattered in the dispersion medium, stirs and form clay dispersion; The emulsifying agent of 1-5 weight part, the initiator of 0.1-1 weight part are dispersed in the dispersion medium, stir adding 100 parts by weight of acrylic ester monomer down, form monomer emulsion; The total weight parts of dispersion medium is 125-135;
2) splash into monomer emulsion after clay dispersion is heated to 70-80 ℃, continue reaction at 80～85 ℃ then, obtain pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material.
Wherein, step 2) splashing into monomer emulsion can be controlled in 3～4 hours and finishes.
The montmorillonite clay interlayer is the very strong sodium ion of hydratability, and polynite can be peeled off into laminated structure with osmotic swelling by crystallographic expansion in its aqueous solution.The present invention utilizes the hydroexpansivity of polynite, is dispersion medium with water, adopts the emulsion intercalation polymerization process to prepare pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material, has avoided the treating processes that organises of polynite, practicality simple to operate; And, part pressure sensitive adhesive matrix polymer enters in the middle of the montmorillonite layer, has strengthened the interaction between inorganics and polymeric matrix, and the physical crosslinking point of matrix material, chemically crosslinked point are increased, this just impels the cross-linking density of matrix material to rise, and cohesive strength increases; Simultaneously because the laminated structure of polynite particle, have good iris action in polymeric matrix, therefore prepared pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material has good pressure-sensitive adhesive performance and good heat-resisting and solvent resistance.The present invention is a dispersion medium with water, has advantages such as environmental protection, economic security, preparation process production efficiency height, and with short production cycle, the gained composite property is good, has wide application prospect.
Embodiment
Embodiment 1
With the cationic exchange total volume is that 100meq/100g, particle diameter are 30 microns clay 1g, adds deionized water 100g, and after waiting to be uniformly dispersed, high-speed stirring 0.5 hour obtains slurry A.2g sodium lauryl sulphate and 0.8g ammonium persulphate are dissolved in the 30g deionized water, and powerful the stirring down adds 95g butyl acrylate, 4g methyl methacrylate and 1g vinylformic acid, forms stable emulsion B.Slurry A is joined in the polymerization reactor, and system vacuumizes, inflated with nitrogen 3 times, last nitrogen protection.System is warmed up to 80 ℃, under the agitation as appropriate speed, in 4 hours, emulsion B is at the uniform velocity splashed among the slurry A; After treating that emulsion B drips off, system is warming up to 84 ℃, constant temperature 2 hours.After cooling, filtration, drying, obtain the polyacrylate pressure-sensitive/clay intercalation composite material of emulsion polymerization prepared.Its performance sees Table 1.
Embodiment 2-5
According to embodiment 1, the preparation clay content is respectively the matrix material of 2g, 3g, 4g, 5g, and its performance sees Table 1.
Embodiment 6 (Comparative Examples)
2g sodium lauryl sulphate and 0.8g ammonium persulphate are dissolved in the 30g deionized water, and powerful the stirring down adds 95g butyl acrylate, 4g methyl methacrylate and 1g vinylformic acid, forms stable emulsion B.The 100g deionized water is joined in the polymerization reactor, and system vacuumizes, inflated with nitrogen 3 times, last nitrogen protection.System is warmed up to 80 ℃, under the agitation as appropriate speed, in 4 hours, emulsion B is at the uniform velocity splashed among the slurry A; After treating that emulsion B drips off, system is warming up to 84 ℃, constant temperature 2 hours.After cooling, filtration, drying, obtain Comparative Examples.Its performance sees Table 1.
The performance of composites table of the different clay contents of table 1.
As seen from Table 1, compare with the polyacrylate pressure-sensitive of no clay, polyacrylate pressure-sensitive/clay intercalation composite material of the present invention has good heat-resistant and solvent resistance.After polynite added, pressure sensitive adhesive was held viscous force and is significantly improved under the prerequisite that keeps just sticking preferably and stripping strength.And along with the wherein increase of clay content, hold viscosity energy, resistance toheat, the solvent resistance etc. of matrix material all increase.The pressure sensitive adhesive utmost point that this class adds polynite is suitable for Application Areass such as surface protection tape, high temperature resistant adhesive tape.
Embodiment 7,
With the cationic exchange total volume is that 100meq/100g, particle diameter are 30 microns clay 2g, adds deionized water 100g, and after waiting to be uniformly dispersed, high-speed stirring 0.5 hour obtains slurry A.1.5g Sodium dodecylbenzene sulfonate and 0.5g Potassium Persulphate are dissolved in the 25g deionized water, and powerful the stirring down adds 90g acrylic acid-2-ethyl-own ester, 9g methyl methacrylate and 1g methacrylic acid, forms stable emulsion B.Slurry A is joined in the polymerization reactor, and system vacuumizes, inflated with nitrogen 3 times, last nitrogen protection.System is warmed up to 80 ℃, under the agitation as appropriate speed, in 4 hours, emulsion B is at the uniform velocity splashed among the slurry A; After treating that emulsion B drips off, system is warming up to 80 ℃, constant temperature 2 hours.After cooling, filtration, drying, obtain the polyacrylate pressure-sensitive/clay intercalation composite material of emulsion polymerization prepared.
Embodiment 8,
With the cationic exchange total volume is that 100meq/100g, particle diameter are 50 microns clay 3g, adds deionized water 100g, and after waiting to be uniformly dispersed, high-speed stirring 0.5 hour obtains slurry A.1g Sodium dodecylbenzene sulfonate, 2g Nonyl pheno base ether and 0.8g Potassium Persulphate are dissolved in the 35g deionized water, and powerful the stirring down adds 97g butyl acrylate, 1g Propylene glycol monoacrylate and 2g vinylformic acid, forms stable emulsion B.Slurry A is joined in the polymerization reactor, and system vacuumizes, inflated with nitrogen 3 times, last nitrogen protection.System is warmed up to 70 ℃, under the agitation as appropriate speed, in 4 hours, emulsion B is at the uniform velocity splashed among the slurry A; After treating that emulsion B drips off, system is warming up to 80 ℃, constant temperature 2 hours.After cooling, filtration, drying, obtain the polyacrylate pressure-sensitive/clay intercalation composite material of emulsion polymerization prepared.
Claims (9)
1, a kind of pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material comprises following components by part by weight:
Acrylate monomer 100,
Clay 1～5,
Dispersion medium 125-135,
Initiator 0.1～1,
Emulsifying agent 1～5.
2, pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material according to claim 1 is characterized in that: described acrylate monomer is selected from one or more in n-butyl acrylate, the positive ethyl ester of vinylformic acid, acrylic acid-2-ethyl-own ester, methyl methacrylate, vinylformic acid, methacrylic acid, Hydroxyethyl acrylate and the Propylene glycol monoacrylate.
3, pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material according to claim 1, it is characterized in that: described clay is a layer aluminosilicate more than 80% for the polynite weight content, particle diameter is 30～50 microns, and the cationic exchange total volume is 80～120meq/100g.
4, pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material according to claim 1 is characterized in that: described dispersion medium is a water.
5, pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material according to claim 1 is characterized in that: described initiator is ammonium persulphate or Potassium Persulphate.
6, according to the arbitrary described pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material of claim 1-5, it is characterized in that: described emulsifying agent is selected from one or more in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate and the Nonyl pheno base ether.
7, the preparation method of the described pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material of claim 1 comprises the steps:
1) the 1-5 parts by weight of clay is scattered in the dispersion medium, stirs and form clay dispersion; The emulsifying agent of 1-5 weight part, the initiator of 0.1-1 weight part are dispersed in the dispersion medium, stir adding 100 parts by weight of acrylic ester monomer down, form monomer emulsion; The total weight parts of dispersion medium is 125-135;
2) splash into monomer emulsion after clay dispersion is heated to 70-80 ℃, continue reaction at 80～85 ℃ then, obtain pressure-sensitive polyacrylate emulsion glue/clay intercalation composite material.
8, preparation method according to claim 7 is characterized in that: described acrylate monomer is selected from one or more in n-butyl acrylate, the positive ethyl ester of vinylformic acid, acrylic acid-2-ethyl-own ester, methyl methacrylate, vinylformic acid, methacrylic acid, Hydroxyethyl acrylate and the Propylene glycol monoacrylate; Described clay is a layer aluminosilicate more than 80% for the polynite weight content, and particle diameter is 30～50 microns, and the cationic exchange total volume is 80～120meq/100g; Described dispersion medium is a water; Described initiator is ammonium persulphate or Potassium Persulphate; Described emulsifying agent is selected from one or more in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate and the Nonyl pheno base ether.
9, according to claim 7 or 8 described preparation methods, it is characterized in that: step 2) the described monomer emulsion that splashes into finished in 3～4 hours.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698784B (en) * | 2009-09-22 | 2012-01-25 | 北京高盟新材料股份有限公司 | Pressure sensitive conductive adhesive composition and preparation method thereof |
| CN102358766A (en) * | 2011-07-28 | 2012-02-22 | 东华大学 | Synthesis method of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion |
| CN101343518B (en) * | 2007-07-11 | 2012-12-05 | 日东电工株式会社 | Adhesive composition, adhesive optical film and image display device |
| CN103666343A (en) * | 2013-12-10 | 2014-03-26 | 四川之江化工新材料有限公司 | Preparation method of bentonite-xanthan gum modified lithium ion battery adhesive |
| CN103965816A (en) * | 2014-05-22 | 2014-08-06 | 中山职业技术学院 | Low-VOC (Volatile Organic Compound) high-performance emulsion adhesive for non-woven fabric material and preparation method thereof |
| CN105643733A (en) * | 2016-01-30 | 2016-06-08 | 临沂山大木业有限公司 | Five-layer plywood and manufacturing method thereof |
| CN107236493A (en) * | 2017-07-15 | 2017-10-10 | 合肥皖水信息科技有限公司 | A kind of Communication Equipment joint pressure sensitive adhesive |
| CN109749668A (en) * | 2019-01-22 | 2019-05-14 | 陕西友日久实业发展有限公司 | A kind of adhesive tape and adhesive tape glue |
-
2005
- 2005-04-15 CN CN 200510064435 patent/CN1847350A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343518B (en) * | 2007-07-11 | 2012-12-05 | 日东电工株式会社 | Adhesive composition, adhesive optical film and image display device |
| CN101698784B (en) * | 2009-09-22 | 2012-01-25 | 北京高盟新材料股份有限公司 | Pressure sensitive conductive adhesive composition and preparation method thereof |
| CN102358766A (en) * | 2011-07-28 | 2012-02-22 | 东华大学 | Synthesis method of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion |
| CN102358766B (en) * | 2011-07-28 | 2013-04-03 | 东华大学 | Synthesis method of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion |
| CN103666343A (en) * | 2013-12-10 | 2014-03-26 | 四川之江化工新材料有限公司 | Preparation method of bentonite-xanthan gum modified lithium ion battery adhesive |
| CN103965816A (en) * | 2014-05-22 | 2014-08-06 | 中山职业技术学院 | Low-VOC (Volatile Organic Compound) high-performance emulsion adhesive for non-woven fabric material and preparation method thereof |
| CN105643733A (en) * | 2016-01-30 | 2016-06-08 | 临沂山大木业有限公司 | Five-layer plywood and manufacturing method thereof |
| CN107236493A (en) * | 2017-07-15 | 2017-10-10 | 合肥皖水信息科技有限公司 | A kind of Communication Equipment joint pressure sensitive adhesive |
| CN109749668A (en) * | 2019-01-22 | 2019-05-14 | 陕西友日久实业发展有限公司 | A kind of adhesive tape and adhesive tape glue |
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