CN1355267A - Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure - Google Patents
Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure Download PDFInfo
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- CN1355267A CN1355267A CN 01144663 CN01144663A CN1355267A CN 1355267 A CN1355267 A CN 1355267A CN 01144663 CN01144663 CN 01144663 CN 01144663 A CN01144663 A CN 01144663A CN 1355267 A CN1355267 A CN 1355267A
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Abstract
An acrylic acid modified polyurethane adhesive with networked "core-shell" structure is prepared through LIPN technique and seed emulsion polymerization. Its latex granularity is adjustable for distrilution in 20-200 mm. Its advantages include high adhesion, excellent resistance to fatigue, impact and abrasion, and wide application range including pressure-sensing adhesive, paint for fabric and leather, high-molecular medical material, passive-sensing package for high energy explosive, etc.
Description
Technical field:
The present invention relates to have the interpenetrating(polymer)networks aqueous polyurethane latex adhesive of " nuclear-shell " structure, belong to the new type bonding agent technical field.
Background technology:
Urethane (PU) emulsion is a dispersion medium with water, has environmentally safe, does not fire low cost and other advantages, is widely used at coating and adhesive field.Comparatively active to the research of PU emulsion in recent years, concentrate on hide finishes but use, tackiness agent, weaving coating and slowly-releasing are isolated the application product of coating material aspect and are studied less.Polyacrylic ester (PA) emulsion is compared with its solvent-borne type product with urethane (PU) emulsion, have inexpensive, safe, do not fire, advantage such as nontoxic, free from environmental pollution, thereby be widely used aspect coating, tackiness agent, printing ink, the fabric finish.But the problem that pure PU emulsion exists is: obdurability, wear resistance, weathering resistance, water tolerance and chemical proofing are poor; And single PU emulsion is in stability, from insufficient place is also arranged aspect the gloss retention of thickening property, solid content, range of application, film.PU/PA has certain complementary action, PU/PA composite emulsion can overcome their shortcomings separately in nature, make the most of the advantage, make emulsion and glued membrane performance be improved significantly, be called as third generation aqueous polyurethane.The method for preparing the PUA composite emulsion has following 3 kinds: (1) PU, PA emulsion blending crosslinking; (2) the unsaturated urethane monomer and the acrylic ester copolymer method of the two keys of anamorphic zone.(3) make the composite emulsion polymerization method etc. of seed with the PU emulsion.Domestic polyurethane binder, the finishing agent of listing in the Chemicals handbook mostly is solvent-borne type at present, the simple polyurethane binder of aqueous dispersion type, along with living standards of the people improve and every profession and trade to the consumers demand of polyurethane material over-all properties, particularly along with the raising of public's environmental consciousness, the green polyurethane binder product of low VOC that exploitation has high additive value has realistic meaning very much; In addition, for certain a little special trades, advance fields such as material as military project, space flight, the substitute of seeking safe ready has become the important directions of functional adhesive development of new generation.Many at present employing solvent methods are produced polyurethane binder, and mostly are single PU emulsion, in stability, and from thickening property, solid content, range of application, shock-resistance and fatigue resistance, there is weak point the damping characteristic aspect more,
Summary of the invention:
A kind of aqueous polyurethane adhesive and polymerization technique have the polyurethane/polyacrylate interpenetrating network feature of " nuclear-shell " structure, adopt LIPN technology and seeded emulsion polymerization, and its latex distributes through grain can be adjustable at 20mm-200mm.
" nuclear-shell " structure is that urethane is at the latex granule skin, polyacrylic ester is at the emulsion particle internal layer, latex particle has tangible phase separation structure, PU gradually reduces to celestial layer from the particle skin, and PA progressively increases mutually, forms the particle core of PA phase enrichment, and PU is a shell, PA forms anti-phase " nuclear-shell " structure for nuclear.
Polymerization technique comprises: preparation earlier contains the polyaminoester emulsion I net of hydrophilic group, then this emulsion is made seed, and adding acrylic monomer and linking agent does not have the saponification letex polymerization, obtains the II net, i.e. PU/PA nuclear-shell mould emulsion.
Polyaminoester emulsion I net is by polyisocyanates, polyvalent alcohol and hydrophilic monomer chain extender and reactive emulsifier monomer, additive and a little diluting solvent reacted under certain condition make.
Polyaminoester emulsion II net is with acrylic monomer, vinylbenzene and specific functionality linking agent monomer and initiator, joins by going in the environment of I net as seed, I net seed is carried out swelling, and carry out the seed emulsion copolymerization, react 40-90 ℃, time 4-6 hour, obtain product.
Above-mentioned polyisocyanates can be TMXDI (-tetramethyl xylene support vulcabond), TDI, MDl, and PAPI, IPDI, and TDl divides 2.4 1 TDl and two kinds of isomer of 2.6 1 TDI; The polyol that uses has polyester polyol, polyether glycol, Viscotrol C and Resins, epoxy.
Described acrylic monomer can be butyl acrylate, methyl methacrylate, propyl acrylate etc.
Polyurethane binder water-based outer core provided by the present invention is by polyisocyanates, polyol, and aliphatic dialcohol class and additive are dissolved in the organic solvent, reacts to form under catalyst action.The polyisocyanates that uses has TDI, MDl, and PAPI, IPDI, TXMDI etc., and TDl divides 2.4-TDl and two kinds of isomer of 2.6-TDI.The polyol that uses has polyester resin, polyether resin, Viscotrol C, Resins, epoxy etc.The aliphatic diol class of using has the 1.3-butyleneglycol, 1.4-butyleneglycol, propylene glycol, ethylene glycol etc.The organic solvent that uses has the ester class, ketone and aromatic hydrocarbon, and halohydrocarbon etc. are generally selected the organic solvent of boiling point between 55-80 ℃ for use.The catalyzer that uses has tertiary amines, organometallic compound and organophosphorus etc.
Route of the present invention is: adopt acetone or butanone to make solvent, carry out polymerization with polyisocyanates, admixtured polyether polyvalent alcohol, carboxylic dihydroxyl compound, make the urethane of band carboxyl, neutralize with tertiary amine again, distillation removes solvent, makes self-emulsifying and double bond containing urethane anionic emulsion.Then with this emulsion as seed, add acrylic ester monomer and an amount of interpenetrating(polymer)networks linking agent monomer carries out letex polymerization, can obtain the core-shell type compounded latex tackiness agent of PA/PA interpenetrating(polymer)networks.The said aqueous polyurethane adhesive of the present invention that Here it is, its part chemical reaction architecture formula is:
R
1, R
2, R
3Can be the hydrocarbon chain with different branched structures, m, n, p can suitably regulate n＞m according to the product estimated performance
When polyurethane binder of the present invention is applied in fabric coating, can use separately, also can use with other material blendings.This polyurethane binder-(NH-CO-O-), show the viscosity and the polarity of height, for synthon, PVC leather surface, reach various materials and have very high adhesive property owing to contain isocyano-(NCO) and carbamate groups in the molecular chain.Can form hydrogen bond between the macromolecular chain simultaneously, make its cohesive strength height, anti-solvent, wear-resisting, adopted special polyester polyether polyol in addition, anti-hydrolytic performance is also better.The isocyanic ester of polymer modification has the molecular linkage of flexibility, thereby very high elasticity is arranged, vibration resistance, and shock resistance, antifatigue, particularly resistance to low temperature is fabulous, is better than other any tackiness agents.This tackiness agent is not only applicable to the PVC leatheroid, also be applicable to weaving, clothes and process industry, and fabric and polyurethane imitation cortex close, the water-proof decorative coating, polyurethane foam is laminated, the frlml laminating of packing and electric insulation, adhering to polyurethane foams is scrubbed pad, is specially adapted to require the jacquard weave flocking of clear profile line.
Description of drawings:
Fig. 1 is the structural models figure of polyurethane binder of the present invention;
Fig. 2 is that polyurethane binder amplifies 42000 times transmission electron microscope photo;
Fig. 3 is that polyurethane binder amplifies 50000 times transmission electron microscope photo;
Fig. 4 is the wall material figure of polyurethane binder microcapsule coating material.
Embodiment:
Synthesizing of double bond containing PU emulsion: according to a certain ratio vulcabond, admixtured polyether polyvalent alcohol, carboxylic dihydroxyl compound are dropped into successively the four neck round-bottomed flasks that reflux condensing tube, thermometer, stirrer are housed, stir, splash into the active emulsifier monomer that contains unsaturated link(age), 80 ℃ of reactions of constant temperature 2-3 hour; React to the NCO Gent and levy absorption peak (2270cm
-1) disappear; Be cooled to 60 ℃ and add HPA (containing hydroquinone of polymerization retarder), add acetone solvent and make the PU performed polymer, add the tertiary amines neutralization then, and add water and stir phase inversion, then add the quadrol chain extension, decompression is at last taken out and is steamed acetone, and it is 30% double bond containing anionic PU emulsion that self-emulsifying makes total solid content.
Synthesizing of PU-PA composite emulsion: emulsifying agent, sodium hydrogen carbonate solution and distilled water are added in the reaction flask, above made PU latex particle is carried out diluted swelling in monomers such as part BA, St, be warming up to 60-80 ℃, logical N
2Protection splashes into and mixes Acrylic Acid Monomer and initiator and an amount of interpenetrating(polymer)networks linking agent monomer, after keeping reacting certain hour under the certain viscosity, is warming up to 85-90 ℃, is incubated 1 hour, is cooled to below 45 ℃ discharging.Through 50-100 order nylon net filter, promptly obtain polyurethane binder of the present invention.The gained emulsion solid content is 40-50%, pH value 5.5-6.5, viscosity 50-150mPas.
Embodiment 1: loomage water proof and moisture permeable is covered with paint, lacquer, colour wash, etc. finishing composition: water-based PU/PA coating-forming agent can be used for dry coating, and finishing technique is covered with paint, lacquer, colour wash, etc. in transfer printing etc., can obtain water tolerance, and principal characteristic is good; Good hand feeling is smooth, and has the finishing effect of ventilation property.Prescription: 1, preceding waterproofing: 100 parts of sumiflouil EM-11 20g/L2, top finish: PU/PA
3 parts of Mirox AM+PVP
5 parts of Teflon289
2 part 3 of MD resin, back arrangement: sumiflouil EM-11 30g/L
Water-resisting agent 40g/L
Catalyzer HA 20g/L technical process: (dry coating)
Before waterproofing (soaks rolls), temperature 100-120 ℃,
Coating, oven dry (100-120 ℃), back waterproofing (two soak two rolls), oven dry (100-120 ℃), bake (150 ℃, 30min) technical process: (transfer method)
Separate-type paper is coated with that surface layer, oven dry (1mm, 100-120 ℃), coating adhesive, base material are bonding, oven dry (150 ℃, 2min), separate-type paper separates, clot
Embodiment 2: the microcapsule cladding process of solid propellant filler: C1-20/ (PU/PA)=95-99%/5-1%, and interface-cross-linked dose, coupling agent, vacuum spray drying (T=50-110 ℃, vacuum tightness: 1.2-5.3 * 10
4Pa), obtaining wall thickness thickness is 0.1um-3um, apparent density: 1.29/cm
3, the powder of good fluidity is convenient to casting processing.
Claims (8)
1, a kind of aqueous polyurethane adhesive and polymerization technique is characterized in that: have the polyurethane/polyacrylate interpenetrating network feature of " nuclear-shell " structure, adopt LIPN technology and seeded emulsion polymerization, its latex particle size distributes can be adjustable at 20mm-200mm.
2, aqueous polyurethane adhesive tackiness agent according to claim 1, it is characterized in that: described " nuclear-shell " structure is that urethane is at the latex granule skin, polyacrylic ester is at the emulsion particle internal layer, latex particle has tangible phase separation structure, and PU gradually reduces to internal layer from the particle skin, and PA progressively increases mutually, form the particle core of PA phase enrichment, PU is a shell, and PA forms anti-phase " nuclear-shell " structure for nuclear.
3, the polymerization technique of polyurethane binder according to claim 1, it is characterized in that: preparation earlier contains the polyaminoester emulsion I net of hydrophilic group, then this emulsion is made seed, and adding acrylic monomer and linking agent does not have the saponification letex polymerization, obtain the II net, i.e. PU/PA nuclear-shell mould emulsion.
4, according to claim 1,3 described polyaminoester emulsion I nets, it is characterized in that: it is by polyisocyanates, polyvalent alcohol and hydrophilic monomer chain extender and reactive emulsifier monomer, additive and a little diluting solvent reacted under certain condition make.
5, according to claim 1,3 described polyaminoester emulsion II nets, it is characterized in that: be acrylic monomer, vinylbenzene and specific functionality linking agent monomer and initiator, join by going in the environment of I net as seed, I net seed is carried out swelling, and carry out the seed emulsion copolymerization, react 40-90 ℃, time 4-6 hour, obtain product.
6, according to claim 1,4 described polyisocyanates, it is characterized in that: can be TMXDI (-tetramethyl xylene support vulcabond), TDI, MDl, PAPI, IPDI, and TDl divides 2.4-TDl and two kinds of isomer of 2.6-TDI; The polyol that uses has polyester polyol, polyether glycol, Viscotrol C and Resins, epoxy.
7, according to right 1,5 described acrylic monomers, it is characterized in that: can be butyl acrylate, methyl methacrylate, propyl acrylate.
8, tackiness agent according to claim 1, it is characterized in that: be particularly suitable for slow-release microcapsule wall material, reach the coating material that promotes tackiness agent and filler interface compatibility in the solid space compositepropellent, and the insensitiveness coating material of high explosive (HMX, RDX, CL-20 and furazan class explosive), and plastic bonded explosive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01144663 CN1355267A (en) | 2001-12-24 | 2001-12-24 | Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01144663 CN1355267A (en) | 2001-12-24 | 2001-12-24 | Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure |
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|---|---|
| CN1355267A true CN1355267A (en) | 2002-06-26 |
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ID=4677746
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|---|---|---|---|
| CN 01144663 Pending CN1355267A (en) | 2001-12-24 | 2001-12-24 | Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295260C (en) * | 2003-05-07 | 2007-01-17 | 北京化工大学 | Prepn process of emulsive interpenetrating thermoplastic elastomer |
| CN100345879C (en) * | 2004-08-03 | 2007-10-31 | 耿耀宗 | New type polyurethane/polyacrylic ester latex interpenetrating network polymer emulsion material and its synthesis technology |
| CN101220192B (en) * | 2007-09-30 | 2010-06-09 | 安徽大学 | Synthesis of fluoridation aquosity polyurethane-polyacrylate composite emulsion |
| CN101165075B (en) * | 2007-09-07 | 2010-06-23 | 香港生产力促进局 | Polyurethane-acrylic ester composite emulsion and preparation method thereof |
| CN101775158A (en) * | 2010-03-12 | 2010-07-14 | 北京橡胶工业研究设计院 | Microencapsulated rubber accessory ingredient |
| CN101805514A (en) * | 2010-03-17 | 2010-08-18 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| CN102533184A (en) * | 2011-12-15 | 2012-07-04 | 广东达美新材料有限公司 | Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof |
| CN102628228A (en) * | 2012-04-12 | 2012-08-08 | 成都德美精英化工有限公司 | Method for synthesizing coating printing thickening agent |
| CN102690398A (en) * | 2011-08-18 | 2012-09-26 | 扬州市伊丽特高分子材料科技有限公司 | Latex and preparation method thereof |
| CN103059230A (en) * | 2013-01-30 | 2013-04-24 | 广东银洋树脂有限公司 | Acrylate modified aqueous polyurethane and preparation method and application thereof |
| CN103421456A (en) * | 2013-07-26 | 2013-12-04 | 伟明树脂制品(博罗)有限公司 | Adhesive and preparation method thereof |
| CN104725570A (en) * | 2015-01-26 | 2015-06-24 | 陈维林 | Latex and preparation method thereof |
| CN104946177A (en) * | 2015-06-27 | 2015-09-30 | 广东远东高分子科技有限公司 | Water-based laminated adhesive and preparation method thereof |
| CN106749831A (en) * | 2016-12-20 | 2017-05-31 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method of environmental protection adhesive |
| CN107695902A (en) * | 2017-10-18 | 2018-02-16 | 河北思瑞恩新材料科技有限公司 | One flocked material and preparation method thereof |
| CN109699642A (en) * | 2018-12-21 | 2019-05-03 | 江苏精禾界面科技有限公司 | A kind of pesticide micro-capsule and preparation method thereof can easily be accommodated rate of release |
| CN111500210A (en) * | 2020-05-20 | 2020-08-07 | 深圳市美信电子有限公司 | Adhesive tape, preparation method and application thereof and medical protective clothing |
| CN112909252A (en) * | 2021-01-19 | 2021-06-04 | 恒大新能源技术(深圳)有限公司 | Polymer binder, its preparation and use |
-
2001
- 2001-12-24 CN CN 01144663 patent/CN1355267A/en active Pending
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295260C (en) * | 2003-05-07 | 2007-01-17 | 北京化工大学 | Prepn process of emulsive interpenetrating thermoplastic elastomer |
| CN100345879C (en) * | 2004-08-03 | 2007-10-31 | 耿耀宗 | New type polyurethane/polyacrylic ester latex interpenetrating network polymer emulsion material and its synthesis technology |
| CN101165075B (en) * | 2007-09-07 | 2010-06-23 | 香港生产力促进局 | Polyurethane-acrylic ester composite emulsion and preparation method thereof |
| CN101220192B (en) * | 2007-09-30 | 2010-06-09 | 安徽大学 | Synthesis of fluoridation aquosity polyurethane-polyacrylate composite emulsion |
| CN101775158A (en) * | 2010-03-12 | 2010-07-14 | 北京橡胶工业研究设计院 | Microencapsulated rubber accessory ingredient |
| CN101805514A (en) * | 2010-03-17 | 2010-08-18 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| CN101805514B (en) * | 2010-03-17 | 2012-01-04 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| CN102690398B (en) * | 2011-08-18 | 2013-12-11 | 扬州市伊丽特高分子材料科技有限公司 | Latex and preparation method thereof |
| CN102690398A (en) * | 2011-08-18 | 2012-09-26 | 扬州市伊丽特高分子材料科技有限公司 | Latex and preparation method thereof |
| CN102533184A (en) * | 2011-12-15 | 2012-07-04 | 广东达美新材料有限公司 | Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof |
| CN102533184B (en) * | 2011-12-15 | 2014-10-15 | 广东达美新材料有限公司 | Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof |
| CN102628228A (en) * | 2012-04-12 | 2012-08-08 | 成都德美精英化工有限公司 | Method for synthesizing coating printing thickening agent |
| CN103059230A (en) * | 2013-01-30 | 2013-04-24 | 广东银洋树脂有限公司 | Acrylate modified aqueous polyurethane and preparation method and application thereof |
| CN103059230B (en) * | 2013-01-30 | 2015-04-15 | 广东银洋树脂有限公司 | Acrylate modified aqueous polyurethane and preparation method and application thereof |
| CN103421456A (en) * | 2013-07-26 | 2013-12-04 | 伟明树脂制品(博罗)有限公司 | Adhesive and preparation method thereof |
| CN104725570A (en) * | 2015-01-26 | 2015-06-24 | 陈维林 | Latex and preparation method thereof |
| CN104946177A (en) * | 2015-06-27 | 2015-09-30 | 广东远东高分子科技有限公司 | Water-based laminated adhesive and preparation method thereof |
| CN106749831A (en) * | 2016-12-20 | 2017-05-31 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method of environmental protection adhesive |
| CN107695902A (en) * | 2017-10-18 | 2018-02-16 | 河北思瑞恩新材料科技有限公司 | One flocked material and preparation method thereof |
| CN107695902B (en) * | 2017-10-18 | 2020-03-06 | 河北思瑞恩新材料科技有限公司 | Flocking material and preparation method thereof |
| CN109699642A (en) * | 2018-12-21 | 2019-05-03 | 江苏精禾界面科技有限公司 | A kind of pesticide micro-capsule and preparation method thereof can easily be accommodated rate of release |
| CN111500210A (en) * | 2020-05-20 | 2020-08-07 | 深圳市美信电子有限公司 | Adhesive tape, preparation method and application thereof and medical protective clothing |
| CN111500210B (en) * | 2020-05-20 | 2023-06-27 | 美信新材料股份有限公司 | Adhesive tape, preparation method and application thereof and medical protective clothing |
| CN112909252A (en) * | 2021-01-19 | 2021-06-04 | 恒大新能源技术(深圳)有限公司 | Polymer binder, its preparation and use |
| CN112909252B (en) * | 2021-01-19 | 2022-05-24 | 恒大新能源技术(深圳)有限公司 | Polymer binder, its preparation and use |
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