CN105199285A - Toughened cyanoacrylate composition - Google Patents
Toughened cyanoacrylate composition Download PDFInfo
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- CN105199285A CN105199285A CN201510772452.6A CN201510772452A CN105199285A CN 105199285 A CN105199285 A CN 105199285A CN 201510772452 A CN201510772452 A CN 201510772452A CN 105199285 A CN105199285 A CN 105199285A
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- cyanoacrylate
- hollow glass
- toughness reinforcing
- glass microbead
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Abstract
The invention discloses a toughened cyanoacrylate composition, which is prepared from the following components in percentage by weight: 50-97% of cyanoacrylate monomer, 0.001-10% of anionic polymerization inhibitor, 0.01-5% of radical polymerization inhibitor, 1-30% parts of hollow glass microbeads and 1-30% of tackifier. The hollow glass microbeads are introduced to the cyanoacrylate composition to enhance the impact resistance of the cyanoacrylate composition. Furthermore, the hollow glass microbeads are subjected to surface modification by using a silane coupling agent, so that the compatibility of the hollow glass microbeads with other component is improved. The hollow glass microbeads are added to the cyanoacrylate monomer to form a good toughening system. The prepared cyanoacrylate composition not only has good toughness, but also has advantage of low cost.
Description
Technical field
The present invention relates to tackiness agent, particularly relate to a kind of toughness reinforcing cyanoacrylate compositions.
Background technology
Cyanoacrylate compositions is a kind of widely used instantaneous adhesive, has curing speed fast, and suitable material is wide, the advantages such as adhesive strength is high, solvent-free, easy to use.But a large shortcoming of this instantaneous adhesive is that property is crisp, and shock resistance is bad, thus limits it and apply widely.Although can carry improve its toughness by adding softening agent in cyanoacrylate compositions, the decline of the performance such as tensile strength and thermotolerance can be caused simultaneously.Current preferred a kind of method for toughening uses heat-resistant powder filler or polyurethane elastomer.Chinese patent CN103555212B relates to a kind of cyanoacrylate compositions of wet-heat resisting, wherein add ASA rubber (multipolymer of vinyl cyanide-vinylbenzene-esters of acrylic acid rubber) as tackifier and toughner, while improving toughening effect, also improve the heat-resisting of instantaneous adhesive and moisture-proof effect.But this rubber toughened method may affect rigidity and the intensity of instantaneous adhesive, also may reduce the thermal conductivity of product.
Summary of the invention
In view of prior art Problems existing and defect, the invention provides a kind of toughness reinforcing cyanoacrylate compositions, to solve the problem of the crisp and impact deficiency of existing cyanoacrylate compositions existence, adopt hollow glass microbead as toughner, curing speed and the shelf life stability of cyanoacrylate compositions can not be affected, can obtain that a kind of cost is lower, the good cyanoacrylate compositions of toughness.
Hollow glass microbead is as a kind of novel rigid inorganic filler toughening polymkeric substance, silicon-dioxide, aluminum oxide, zirconium white, magnesium oxide and water glass etc. are contained by Chemical Composition, have light weight, thermal conductivity low, nontoxic, do not fire, the advantages such as chemical stability is good, corrosion-resistant, are widely used in industry member.The present invention, by carrying out effective coated process to hollow glass microbead surface, as the filling components of instantaneous adhesive, realizes the enhancing to instantaneous adhesive, toughness reinforcing and reduce costs.
In order to solve the problems of the technologies described above, the technical scheme that the present invention takes is: a kind of toughness reinforcing cyanoacrylate compositions, it is characterized in that: described cyanoacrylate compositions is by weight percentage, composed of the following components: cyanoacrylate monomer 50-97%; Anionoid polymerization stopper 0.001-10%; Radical polymerization stopper 0.01-5%; Hollow glass microbead 1-30%; Tackifier 1-30%.
By weight percentage, described cyanoacrylate monomer is 70-90% in the present invention; Anionoid polymerization stopper is 0.001-1%; Radical polymerization stopper is 0.1-1%; Hollow glass microbead is 1-20%.
Cyanoacrylate monomer of the present invention selects one or more in 2-Methyl 2-cyanoacrylate, 2-cyanacrylate, 2-cyanoacrylate propyl propionate, 2-Tisuacryl, 2-alpha-cyanoacrylate methoxy acrylate, 2-alpha-cyanoacrylate ethoxy ethyl ester, 2-alpha-cyanoacrylate methoxyl group propyl ester.
One or more in sulfurous gas, boron trifluoride complex, tosic acid, methylsulfonic acid selected by anionoid polymerization stopper of the present invention.
Radical polymerization stopper of the present invention is one or more in quinone, Resorcinol, p methoxy phenol.
Hollow glass microbead of the present invention is micron order, and its particle size range is at 10-150 micron.
Hollow glass microbead of the present invention uses silane coupling agent to carry out finishing, and this silane coupling agent is the one in Silane coupling agent KH550, silane coupling agent KH560, Silane coupling reagent KH-570, and its consumption is the 1-2% of hollow glass microbead quality.
Of the present inventionly to the process that hollow glass microbead carries out finishing be: first hollow glass microbead is placed in 100-120 DEG C of baking oven dry; Then be added in the ethanolic soln of silane coupling agent, be uniformly mixed post-heating to 40-60 DEG C, supersound process 60min, reheat to 80-110 DEG C, be cooled to room temperature for subsequent use.
One or more in polymethylmethacrylate, polybutylcyanoacrylate, cellulose acetate, acrylic elastomer, Polyvinylalkylethers, aerosil selected by tackifier of the present invention.
The beneficial effect that the present invention produces is: be incorporated into by hollow glass microbead in cyanoacrylate compositions, utilizes hollow glass microbead to strengthen the shock resistance of cyanoacrylate compositions.Further, hollow glass microbead uses silane coupling agent to carry out finishing, improves the consistency of hollow glass microbead and other components.Hollow glass microbead adds in cyanoacrylate monomer can form good toughened system.The cyanoacrylate compositions adopting the present invention to prepare, not only has good toughness, and has the low advantage of cost.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
The present invention using 2-cyanacrylate as the preferred monomers for the preparation of the toughness reinforcing cyanoacrylate compositions of hollow glass microbead; The preferred sulfurous gas of anionoid polymerization stopper; The preferred Resorcinol of radical polymerization stopper; The preferred polymethylmethacrylate of tackifier (PMMA).
The cyanoacrylate compositions utilizing hollow glass microbead toughness reinforcing provided by the invention can also comprise other auxiliary agents, and other auxiliary agents are softening agent, promotor, linking agent, coupling agent, tinting material or heat-resisting additive.
First the present invention carries out finishing to hollow glass microbead, and its preparation process is: first commercially available hollow glass microbead is placed in 110 DEG C of baking ovens dry; Then be added in the ethanolic soln of KH-550 silane coupling agent (20wt%), wherein the consumption of KH-550 silane coupling agent is 1% of hollow glass microbead quality; Be uniformly mixed post-heating to 50 DEG C, supersound process 60min, reheat to 100 DEG C, be cooled to room temperature after thorough Ex-all ethanol for subsequent use.
Embodiment 1:
Be add the anionoid polymerization stopper sulfurous gas of 0.005%, radical polymerization hydroquinone of polymerization retarder, the polymethylmethacrylate (PMMA) of 5%, the hollow glass microbead of 5% of 0.1% in the ethyl cyanoacrylate monomer of 89.895% at weight content, joining mixing and stirring in glue still, obtained glue.
Test adhesive shear strength (25 DEG C): No. 45 steel are 22.1MPa, and aluminium is 20.7Mpa.
Embodiment 2:
Be add the anionoid polymerization stopper sulfurous gas of 0.05%, radical polymerization hydroquinone of polymerization retarder, the polymethylmethacrylate (PMMA) of 15%, the hollow glass microbead of 10% of 0.1% in the ethyl cyanoacrylate monomer of 74.85% at weight content, joining mixing and stirring in glue still, obtained glue.
Test adhesive shear strength (25 DEG C): No. 45 is 25.7MPa, and aluminium is 22.9Mpa.
Embodiment 3:
Be add the anionoid polymerization stopper sulfurous gas of 0.5%, radical polymerization hydroquinone of polymerization retarder, the polymethylmethacrylate (PMMA) of 20%, the hollow glass microbead of 15% of 0.1% in the ethyl cyanoacrylate monomer of 64.4% at weight content, joining mixing and stirring in glue still, obtained glue.
Test adhesive shear strength (25 DEG C): No. 45 steel are 19.3MPa, and aluminium is 18.7Mpa.
Embodiment 4(comparative example):
Be anionoid polymerization stopper sulfurous gas, the radical polymerization hydroquinone of polymerization retarder of 0.1%, the polymethylmethacrylate (PMMA) of 25% of interpolation 0.05% in the ethyl cyanoacrylate monomer of 74.85% at weight content, joining mixing and stirring in glue still, obtained glue.
Test adhesive shear strength (25 DEG C): No. 45 steel are 18.3MPa, and aluminium is 17.9Mpa.
Embodiment 5:
Be anionoid polymerization stopper sulfurous gas, the radical polymerization hydroquinone of polymerization retarder of 0.05%, the polymethylmethacrylate (PMMA) of 2% of interpolation 0.05% in the ethyl cyanoacrylate monomer of 95.9% at weight content, the hollow glass microbead of 2%, joining mixing and stirring in glue still, obtained glue.
Test adhesive shear strength (25 DEG C): No. 45 steel are 18.7MPa, and aluminium is 17.1Mpa.
Embodiment 6:
Be anionoid polymerization stopper sulfurous gas, the radical polymerization hydroquinone of polymerization retarder of 1%, the polymethylmethacrylate (PMMA) of 2% of interpolation 0.05% in the ethyl cyanoacrylate monomer of 94.95% at weight content, the hollow glass microbead of 2%, joining mixing and stirring in glue still, obtained glue.
Test adhesive shear strength (25 DEG C): No. 45 steel are 17.7MPa, and aluminium is 18.5Mpa.
As can be seen from the above embodiments: hollow glass microbead can strengthen the adhesive shear strength of cyanoacrylate, namely improves toughness; When hollow glass microbead content is 10%, toughening effect is optimum, and content is too much or very fewly all can reduce toughening effect.
Claims (9)
1. a toughness reinforcing cyanoacrylate compositions, is characterized in that: described cyanoacrylate compositions is by weight percentage, composed of the following components: cyanoacrylate monomer 50-97%; Anionoid polymerization stopper 0.001-10%; Radical polymerization stopper 0.01-5%; Hollow glass microbead 1-30%; Tackifier 1-30%.
2. a kind of toughness reinforcing cyanoacrylate compositions according to claim 1, is characterized in that: by weight percentage, and described cyanoacrylate monomer is 70-90%; Anionoid polymerization stopper is 0.001-1%; Radical polymerization stopper is 0.1-1%; Hollow glass microbead is 1-20%.
3. a kind of toughness reinforcing cyanoacrylate compositions according to claim 1, is characterized in that: described cyanoacrylate monomer selects one or more in 2-Methyl 2-cyanoacrylate, 2-cyanacrylate, 2-cyanoacrylate propyl propionate, 2-Tisuacryl, 2-alpha-cyanoacrylate methoxy acrylate, 2-alpha-cyanoacrylate ethoxy ethyl ester, 2-alpha-cyanoacrylate methoxyl group propyl ester.
4. a kind of toughness reinforcing cyanoacrylate compositions according to claim 1, is characterized in that: one or more in sulfurous gas, boron trifluoride complex, tosic acid, methylsulfonic acid selected by described anionoid polymerization stopper.
5. a kind of toughness reinforcing cyanoacrylate compositions according to claim 1, is characterized in that: described radical polymerization stopper is one or more in quinone, Resorcinol, p methoxy phenol.
6. a kind of toughness reinforcing cyanoacrylate compositions according to claim 1, is characterized in that: described hollow glass microbead is micron order, and its particle size range is at 10-150 micron.
7. a kind of toughness reinforcing cyanoacrylate compositions according to claim 6, it is characterized in that: described hollow glass microbead uses silane coupling agent to carry out finishing, this silane coupling agent is the one in Silane coupling agent KH550, silane coupling agent KH560, Silane coupling reagent KH-570, and its consumption is the 1-2% of hollow glass microbead quality.
8. a kind of toughness reinforcing cyanoacrylate compositions according to claim 7, is characterized in that: the process of hollow glass microbead being carried out to finishing is: first hollow glass microbead is placed in 100-120 DEG C of baking oven dry; Then be added in the ethanolic soln of silane coupling agent, be uniformly mixed post-heating to 40-60 DEG C, supersound process 60min, reheat to 80-110 DEG C, be cooled to room temperature for subsequent use.
9. a kind of toughness reinforcing cyanoacrylate compositions according to claim 1, is characterized in that: one or more in polymethylmethacrylate, polybutylcyanoacrylate, cellulose acetate, acrylic elastomer, Polyvinylalkylethers, aerosil selected by described tackifier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510772452.6A CN105199285A (en) | 2015-11-12 | 2015-11-12 | Toughened cyanoacrylate composition |
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| CN201510772452.6A CN105199285A (en) | 2015-11-12 | 2015-11-12 | Toughened cyanoacrylate composition |
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| CN105199285A true CN105199285A (en) | 2015-12-30 |
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| CN201510772452.6A Pending CN105199285A (en) | 2015-11-12 | 2015-11-12 | Toughened cyanoacrylate composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591569A (en) * | 2019-09-17 | 2019-12-20 | 浙江派菲特新材料科技有限公司 | Environment-friendly low-whitening instant adhesive |
| CN116731666A (en) * | 2023-08-15 | 2023-09-12 | 山东凯恩新材料科技有限公司 | Waterproof quick-drying adhesive and preparation method thereof |
| CN117298328A (en) * | 2023-11-30 | 2023-12-29 | 四川国屹医疗科技有限公司 | Medical adhesive |
Citations (3)
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| CN101418105A (en) * | 2008-08-28 | 2009-04-29 | 广东联塑科技实业有限公司 | Hollow glass micro bead reinforcement rigid polyvinyl chloride material and preparation method thereof |
| CN102504708A (en) * | 2011-11-07 | 2012-06-20 | 北京天山新材料技术股份有限公司 | Toughened alpha-cyanoacrylate adhesive and preparation method thereof |
| US20120322947A1 (en) * | 2006-10-05 | 2012-12-20 | Loctite (R&D) Limited | Toughened cyanoacrylate compositions |
-
2015
- 2015-11-12 CN CN201510772452.6A patent/CN105199285A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120322947A1 (en) * | 2006-10-05 | 2012-12-20 | Loctite (R&D) Limited | Toughened cyanoacrylate compositions |
| CN101418105A (en) * | 2008-08-28 | 2009-04-29 | 广东联塑科技实业有限公司 | Hollow glass micro bead reinforcement rigid polyvinyl chloride material and preparation method thereof |
| CN102504708A (en) * | 2011-11-07 | 2012-06-20 | 北京天山新材料技术股份有限公司 | Toughened alpha-cyanoacrylate adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李子东等: "《胶黏剂助剂》", 30 June 2009, 化学工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591569A (en) * | 2019-09-17 | 2019-12-20 | 浙江派菲特新材料科技有限公司 | Environment-friendly low-whitening instant adhesive |
| CN116731666A (en) * | 2023-08-15 | 2023-09-12 | 山东凯恩新材料科技有限公司 | Waterproof quick-drying adhesive and preparation method thereof |
| CN116731666B (en) * | 2023-08-15 | 2023-10-20 | 山东凯恩新材料科技有限公司 | Waterproof quick-drying adhesive and preparation method thereof |
| CN117298328A (en) * | 2023-11-30 | 2023-12-29 | 四川国屹医疗科技有限公司 | Medical adhesive |
| CN117298328B (en) * | 2023-11-30 | 2024-03-08 | 四川国屹医疗科技有限公司 | Medical adhesive |
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Application publication date: 20151230 |