WO2012154132A2 - Adhésif/agent d'étanchéité utilisé de préférence pour panneaux de construction - Google Patents

Adhésif/agent d'étanchéité utilisé de préférence pour panneaux de construction Download PDF

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Publication number
WO2012154132A2
WO2012154132A2 PCT/SI2012/000028 SI2012000028W WO2012154132A2 WO 2012154132 A2 WO2012154132 A2 WO 2012154132A2 SI 2012000028 W SI2012000028 W SI 2012000028W WO 2012154132 A2 WO2012154132 A2 WO 2012154132A2
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WO
WIPO (PCT)
Prior art keywords
adhesive
sealant
vol
hollow microspheres
mineral
Prior art date
Application number
PCT/SI2012/000028
Other languages
English (en)
Other versions
WO2012154132A4 (fr
WO2012154132A3 (fr
Inventor
Mojca Japelj FIR
Bojan BRATUŽ
Aleš KRALJ
Ada BEGUŠ
Original Assignee
Cbs Inśtitut, Celovite Gradbene Reśitve, D.O.O.
Tkk Proizvodnja Kemičnih Izdelkov Srpenica Ob Soči D.D.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cbs Inśtitut, Celovite Gradbene Reśitve, D.O.O., Tkk Proizvodnja Kemičnih Izdelkov Srpenica Ob Soči D.D. filed Critical Cbs Inśtitut, Celovite Gradbene Reśitve, D.O.O.
Priority to EP12756837.6A priority Critical patent/EP2707444A2/fr
Publication of WO2012154132A2 publication Critical patent/WO2012154132A2/fr
Publication of WO2012154132A3 publication Critical patent/WO2012154132A3/fr
Publication of WO2012154132A4 publication Critical patent/WO2012154132A4/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles

Definitions

  • Adhesive/sealant preferably used for construction panels
  • Adhesive/sealant according to this invention has at least equal chemical and mechanical properties as comparable materials known in state of the art, however with lower conductivity which does not exceed 0.30 W/m .
  • Construction panel is insulated glass unit (IGU) or gas filled insulation construction panel (GFP) comprised of one or more chambers to be used in building envelopes - integrated facades or curtain walls and windows. It should be sealed with adhesive/sealant. Adhesives/sealants are most often in forms of putties. Adhesive/sealant are well known in the area of IGUs or GFPs used for fixing of metal frame between two boards and prevention of gas leak from insulation core. The thermal resistance of these IGUs or GFPs is very important for reduction of energy consumption. One of prevalent development direction was reduction of thermal conductivity of metal frame or spacer using hybrid (metal-plastic) materials.
  • the thermal conductivity of adhesive/sealant as known in state of the art is between 0.35 to 0.40 mW/k.
  • the first group shows sealants based on polymers such as polysulfides, polymercaptans, silicones, polyurethanes, and their use in construction specifically as secondary sealant for IGUs or GFPs used for use in building envelopes - integrated facades or curtain walls or windows: US2543844, US2589151 , US4153594, US3689450, US6919397, CA2085077, EP1044936, US5430192, EP0097005, and EP0010888.
  • sealants based on liquid polysulfide polymer, chosen plasticizer and adhesion promoter usually from group of silanes is used today for these purposes.
  • the second group represents sealing materials decreasing their density by use of hollow microspheres into their structure: US4582756, US6915987, and US7067612.
  • the same group includes patents in which the sealing masses are used which by inclusion of hollow microspheres into their structure achieve lower density and better mechanical properties such as tear strength, tensile strength, higher elasticity, resistance to fuels: US20040097643, WO2010019561, and US5663219.
  • Hardened or non-hardened sealing mass with lower density is appropriate for use in different areas: aerospace industry, transport industry (trains, ships, and vehicles), mechanical engineering, construction, civil engineering - anywhere where reduction of mass is important.
  • this mass was not tested for use in the area of IGUs and GFPs.
  • the authors did not involve themselves into questions whether their sealing masses reduce gas permeation (water vapor, argon) which is of key importance in the area of IGUs and GFPs. Their description does not show ability to provide for desired thermal conductivity of sealing masses as their product was not foreseen in energy efficient buildings.
  • the third group show one patent, namely US7569626, describing use of hollow or gas filled glass or ceramic microspheres for achieving lower thermal conductivity of biocompatible polymer used in medical therapies showing overheating due to electric power conduction.
  • the patent does not mention thermal conductivity of polymer however, thermal conductivity of filler is mentioned, said thermal conductivity lower than 5 W/mK, preferably less than 2 W/mK.
  • Said patent is in view of technical field of this invention a distant prior art as it is limited to biocompatible polymers for use in medicine.
  • the research resulting in this patent the polymer adhesive/sealant with lower thermal conductivity for use in construction was developed, said field requiring specific technical and mechanical properties.
  • Cited patent does not give information if described polymer mass provides for key technical requirements to be used as secondary sealant for IGUs and GFPs such as: tensile strength > 0.6 MPa, elongation at break > 50%, hardness according to Shore A > 30.
  • Panel for use in construction industry solves the above presented technical problem by the help of surprising technical effect in that, inter alia, the frame is sealed with a sealant based on silicone or polysulfide.
  • the thermal conductivity of the adhesive/sealant is less than 0.30 W/mK, preferably less than 0.25 W/mK.
  • the adhesive/sealant contains organic and/or mineral hollow microspheres.
  • Adhesive/sealant according to invention was made based on polysulfide or silicone and/or their derivatives, and includes hollow mineral and/or organic microspheres and other fillers enabling achieving lower thermal conductivity of the material.
  • thermal conductivity of the adhesive/sealant below 0.30 W/mK one observes significant improvement in thermal resistance of the frame of IGU or GFP.
  • thermal conductivity of the sealing mass By further reduction of thermal conductivity of the sealing mass the thermal resistance of the frame of IGU or GFP improves, however to achieve the desired mechanical properties of the sealant and the economics of the product optimal thermal conductivity of the sealant should be around 0.25 W/mK.
  • Hollow microspheres are expanded closed cell structures or hollow spherical fillers or ovoid shapes ranging in size from 5 to 500 micrometers. Hollow microspheres can also be filled with gas (eg C02, Ar). Hollow microspheres can be based on minerals (glass, ceramics) or based on organic polymers (PE, PU, PS, PMMA). Examples of suitable mineral hollow microspheres are: Eurocell of Europerla, E-spheres of Envirospheres. Example of suitable organic hollow microspheres is Expancel from Akzo Nobel.
  • the minimum size of mineral hollow microspheres available on the market is 5 ⁇ while maximum size is up to 500 ⁇ .
  • the minimum size of the organic hollow microspheres available on the market is 10 ⁇ , and maximum size up to 1000 ⁇ ⁇ ⁇ .
  • the mixture would be dominated by the smallest mineral and organic hollow microspheres because their thermal conductivity is significantly higher given the large microspheres.
  • Two component adhesives/sealants are commonly used in IGUs and GFPs for fixing the metal frame between two boards and preventing the escape of the gas from the insulating core.
  • Two component adhesive/sealant offer substantially better vapor and gas barrier compared to those with one component adhesive/sealants. Fillers that are built into the two component adhesive/sealant should not exceed the size of 500 ⁇ as this could lead to a clogged or malfunctioning of processing equipment. An even greater problem is the abrasion damage to the metering and mixing systems which are emphasized with increase of size and number of solid particles. Additional problem with mineral hollow microspheres is their fragility as they may crush at too high pressures and high mixing velocity.
  • suitable size for the hollow microspheres is around 300 micrometers.
  • Layer thickness of a secondary seal for IGU and GFP is up to 4 mm. It was empirically determined that the particles must be at least 10 times smaller than the thickness of the layer to achieve the even appearance of secondary seal. If there is a requirement for a smoother appearance of the secondary seal one should use even smaller microspheres under 150 micrometers or even less than 100 micrometers.
  • Particles size - microspheres and fillers - have effect on the mechanical and thermal properties of adhesives/sealants.
  • fillers such as calcium carbonate (calcite, chalk), calcium sulphate (gypsum), clay, mica, and others.
  • calcite, chalk calcium carbonate
  • gypsum calcium sulphate
  • clay clay
  • mica and others.
  • fillers in sealants are the price because adding them significantly reduces the price of adhesive/sealant.
  • Adhesive/sealant without fillers becomes commercially unattractive due to the high price.
  • fillers one achieves the desired tensile modulus. It means that with the combination of different kind of fillers one can obtain the desired hardness, tensile strength, adhesion and viscosity which should be met by the adhesive/sealant to be used in the IGUs and GFPs.
  • secondary sealants for IGUs and GFPs contains 35-50 wt. % of liquid component and 50-65 wt. % fillers, mostly CaC0 3 which may be ground (GCC) or has been treated and precipitated (PCC). Due to the crystal structure and shape the calcium carbonate may have thermal conductivity of 2.4 to 9 W/mK. The larger the particles and quantity of calcium carbonate in the adhesive/sealing mass, the higher its thermal conductivity.
  • the PCC filler loadings in adhesive/sealant formulation typically range from 5 to 15 wt. %, and GCC filler loadings range from 50 to 60 wt. %.
  • the hollow microspheres were used as a substitute for the filler resulting in significant change of ratio of other fillers, especially CaC0 3 to achieve the desired mechanical properties.
  • the research has shown that the thermal conductivity of the adhesive/sealants can be reduced under 0.30 W/mK if at least 5 volumetric percent of conventional fillers in the adhesive/sealing mass are replaced with hollow microspheres.
  • This has of course broken down the standard mass ratio of liquid and solid components in the adhesive/sealing mass as the hollow microspheres have significantly lower density and significantly higher specific surface area making it necessary to use more liquid components, in particular polymer for the hollow microspheres to be mixed into adhesive/sealant.
  • the upper limit of hollow microspheres is around 60 vol. % relative to the total sealant volume. At this value the adhesive/sealant mass at the beginning of curing process is barely flowing, and when it has cured it meets the conditions required by standards in the area of IGUs and GFPs.
  • Organic and mineral microspheres can also be used together in adhesive/sealant according to this invention.
  • the advantage of organic microspheres is that they contribute to lower thermal conductivity more than inorganic microspheres and are less sensitive to the mixing system.
  • the advantage of mineral microspheres is to lower the enthalpy of combustion.
  • the volume ratio of both types of microspheres together in the adhesive/sealing mass retain similar as to the volume ratio of single type of microspheres.
  • the thermal conductivity is important in these applications as well, and is achieved similarly as described earlier.
  • the self-extinguishing properties of the mass is achieved by additives reducing the combustion enthalpy such as Al(OH) 3 and Mg(OH) 2 and additives suppressing the fire in gas phase: halogenated compounds (e.g. Saytex 8010, Albemarle) and antimony oxides, and substances that form an inert layer: ammonium polyphosphate, melamine and polyol (eg dipentaeritriol).
  • the materials of Table 1 were mixed at room temperature in planetary mixer DREIS 1L at 60 rpm. First, the liquid components were mixed (3 to 5 min), and later calcium carbonate was added in portions from finest granulation to the largest. After all the fillers were mixed into the mixture, the vacuum mixing was performed for additional 20 minutes.
  • component B The materials for the preparation of component B were mixed by a laboratory mixer SPEED MIXER FVZ 400 at 2000 rpms 2-times for 30 seconds. Between the two mixing the mass was also hand mixed.
  • Example 2 We prepared two component adhesive/sealant based on polysulfide mixed with mineral hollow microspheres. Composition of component A according to weight and volume fraction is given in Table 3.
  • the materials of Table 3 were mixed at room temperature in planetary mixer DREIS 1L at 60 rpm. First, the liquid components were mixed (3 to 5 min), and later calcium carbonate was added in portions from finest granulation to the largest. After all the fillers were mixed into the mixture, the vacuum mixing was performed for additional 20 minutes. At the end microspheres Eurocell 140-23 were added. They were mixed into the mixture for 1 minute and vacuum mixed for another 5 minutes.
  • Example 3 We prepared two component adhesive/sealant based on polysulfide mixed with organic hollow microspheres. Composition of component A according to weight and volume percent is given in Table 4.
  • the materials as given in Table 4 were mixed at room temperature in planetary mixer DREIS 1L at 60 rpm. First, the liquid components were mixed (3 to 5 min). As the first filler Expancel 461 DET 40 d25 was mixed into the mixture, and then calcium carbonate was added in portions from finest granulation to the largest. After all the fillers were mixed into the mixture, the vacuum mixing was performed for additional 20 minutes.
  • Example 4 We prepared two component adhesive/sealant based on polysulfide mixed with organic and mineral hollow microspheres. Composition of component A according to weight and volume percent is given in Table 5.
  • the materials as given in Table 4 were mixed at room temperature in planetary mixer DREIS 1L at 60 rpm. First, the liquid components were mixed (3 to 5 min). As the first filler Expancel 461 DET 40 d25 was mixed into the mixture, and then calcium carbonate was added in portions from finest granulation to the largest. After all the fillers were mixed into the mixture, the vacuum mixing was performed for additional 20 minutes. At the end microspheres Eurocell 140-23 were added. They were added into the mixture in 1 minute and further vacuum mixed for another 5 minutes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Fireproofing Substances (AREA)

Abstract

L'invention porte sur un adhésif/agent d'étanchéité présentant une moindre conductivité thermique qui est utilisé pour des unités de verre isolées (IUG) et des panneaux de construction d'isolation remplis de gaz (GFP), et lequel adhésif/agent d'étanchéité comprend des microsphères minérales et/ou organiques creuses dans sa structure. La conductivité thermique de l'adhésif/agent d'étanchéité est inférieure à 0,30 W/mK, et, de préférence, inférieure à 0,25 W/mK. Les propriétés chimiques et mécaniques de cette masse d'adhésif/agent d'étanchéité sont comparables à celles des agents d'étanchéité existants utilisés pour des unités de verre isolées et des panneaux de construction d'isolation remplis de gaz.
PCT/SI2012/000028 2011-05-09 2012-05-04 Adhésif/agent d'étanchéité utilisé de préférence pour panneaux de construction WO2012154132A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12756837.6A EP2707444A2 (fr) 2011-05-09 2012-05-04 Adhésif/agent d'étanchéité utilisé de préférence pour panneaux de construction

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SIP-201100150 2011-05-09
SI201100150A SI23731A (sl) 2011-05-09 2011-05-09 Lepilno tesnilna masa prednostno za uporabo v panelu za uporabo v gradbeništvu

Publications (3)

Publication Number Publication Date
WO2012154132A2 true WO2012154132A2 (fr) 2012-11-15
WO2012154132A3 WO2012154132A3 (fr) 2013-08-15
WO2012154132A4 WO2012154132A4 (fr) 2013-10-10

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EP (1) EP2707444A2 (fr)
SI (1) SI23731A (fr)
WO (1) WO2012154132A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018067443A1 (fr) * 2016-10-06 2018-04-12 3M Innovative Properties Company Compositions durcissables et procédés associés
WO2019032856A1 (fr) * 2017-08-11 2019-02-14 Winpak Portion Packaging, Inc. Système et procédé de thermoscellage d'emballage alimentaire
CN110922935A (zh) * 2019-12-07 2020-03-27 杭州之江新材料有限公司 一种双组份有机硅密封胶及在充气中空玻璃中的应用
CN112680174A (zh) * 2020-12-25 2021-04-20 郑州圣莱特空心微珠新材料有限公司 改性硅酮胶及其制备方法和应用、真空玻璃

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106634768B (zh) * 2016-12-14 2020-08-14 湖北回天新材料股份有限公司 浸水粘接性能优异的硅烷改性聚醚密封胶及其制备方法

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US2589151A (en) 1946-09-12 1952-03-11 Standard Oil Dev Co Thioglycolic acid adducts of rubber-like polymers and process of preparing same
US3689450A (en) 1970-10-29 1972-09-05 Phillips Petroleum Co Method of preparing sealants from polybutadiene and mercapto hydroxy compounds
US4153594A (en) 1976-04-08 1979-05-08 Wilson Jr Floyd Insulated glass and sealant therefore
EP0010888A1 (fr) 1978-10-23 1980-05-14 Thiokol Corporation Compositions durcissables en matières solides caoutchouteuses, produits de réaction élastomères à partir de celles-ci et articles comprenant de tels produits de réaction
EP0097005A2 (fr) 1982-06-11 1983-12-28 Morton Thiokol, Inc. Compositions d'étanchéité modifiées par des thioéthers et objets de verre isolés collés avec ces compositions
US4582756A (en) 1983-07-12 1986-04-15 Matsumoto Yushi-Seiyaku Co., Ltd. Organic microballoon
CA2085077A1 (fr) 1991-12-19 1993-06-20 Andrea Wilford Resines epoxy modifiees au polysulfure
US5430192A (en) 1993-08-26 1995-07-04 Morton International, Inc. Polysulfide sealants with reduced moisture vapor transmission
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EP1044936A2 (fr) 1999-04-15 2000-10-18 Rohm And Haas Company Matériau d'étanchéité en polyuréthane basé sur polysulphide pour vitrage isolante
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US6915987B2 (en) 1999-04-20 2005-07-12 Bae Systems Plc. Method of sealing a panel to an aircraft structure
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US7067612B2 (en) 2003-01-30 2006-06-27 Prc-Desoto International, Inc. Preformed compositions in shaped form
US7569626B2 (en) 2003-06-05 2009-08-04 Dfine, Inc. Polymer composites for biomedical applications and methods of making
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2543844A (en) 1945-08-27 1951-03-06 Phillips Petroleum Co Plasticizing synthetic rubber with a reaction product of an alkyl mercaptan and a rubbery diolefin polymer
US2589151A (en) 1946-09-12 1952-03-11 Standard Oil Dev Co Thioglycolic acid adducts of rubber-like polymers and process of preparing same
US3689450A (en) 1970-10-29 1972-09-05 Phillips Petroleum Co Method of preparing sealants from polybutadiene and mercapto hydroxy compounds
US4153594A (en) 1976-04-08 1979-05-08 Wilson Jr Floyd Insulated glass and sealant therefore
EP0010888A1 (fr) 1978-10-23 1980-05-14 Thiokol Corporation Compositions durcissables en matières solides caoutchouteuses, produits de réaction élastomères à partir de celles-ci et articles comprenant de tels produits de réaction
EP0097005A2 (fr) 1982-06-11 1983-12-28 Morton Thiokol, Inc. Compositions d'étanchéité modifiées par des thioéthers et objets de verre isolés collés avec ces compositions
US4582756A (en) 1983-07-12 1986-04-15 Matsumoto Yushi-Seiyaku Co., Ltd. Organic microballoon
CA2085077A1 (fr) 1991-12-19 1993-06-20 Andrea Wilford Resines epoxy modifiees au polysulfure
US5430192A (en) 1993-08-26 1995-07-04 Morton International, Inc. Polysulfide sealants with reduced moisture vapor transmission
US5663219A (en) 1994-05-27 1997-09-02 Morton International, Inc. Lightweight sealant having improved peel strength
EP1044936A2 (fr) 1999-04-15 2000-10-18 Rohm And Haas Company Matériau d'étanchéité en polyuréthane basé sur polysulphide pour vitrage isolante
US6915987B2 (en) 1999-04-20 2005-07-12 Bae Systems Plc. Method of sealing a panel to an aircraft structure
US6919397B2 (en) 2000-05-23 2005-07-19 Henkel-Teroson Gmbh (Henkel-Teroson) Two-component polysulphide adhesive/sealant
US20040097643A1 (en) 2001-04-06 2004-05-20 Peter Bons Low-density sealing mass, ground mass and method for producing the same and the use thereof
US7067612B2 (en) 2003-01-30 2006-06-27 Prc-Desoto International, Inc. Preformed compositions in shaped form
US7569626B2 (en) 2003-06-05 2009-08-04 Dfine, Inc. Polymer composites for biomedical applications and methods of making
WO2010019561A1 (fr) 2008-08-13 2010-02-18 Ppg Industries Ohio, Inc. Particules légères et compositions les contenant

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018067443A1 (fr) * 2016-10-06 2018-04-12 3M Innovative Properties Company Compositions durcissables et procédés associés
CN109790291A (zh) * 2016-10-06 2019-05-21 3M创新有限公司 可固化组合物和相关方法
US10815408B2 (en) 2016-10-06 2020-10-27 3M Innovative Properties Company Curable compositions and related methods
CN109790291B (zh) * 2016-10-06 2021-09-17 3M创新有限公司 可固化组合物和相关方法
WO2019032856A1 (fr) * 2017-08-11 2019-02-14 Winpak Portion Packaging, Inc. Système et procédé de thermoscellage d'emballage alimentaire
CN110922935A (zh) * 2019-12-07 2020-03-27 杭州之江新材料有限公司 一种双组份有机硅密封胶及在充气中空玻璃中的应用
CN112680174A (zh) * 2020-12-25 2021-04-20 郑州圣莱特空心微珠新材料有限公司 改性硅酮胶及其制备方法和应用、真空玻璃

Also Published As

Publication number Publication date
EP2707444A2 (fr) 2014-03-19
WO2012154132A4 (fr) 2013-10-10
WO2012154132A3 (fr) 2013-08-15
SI23731A (sl) 2012-11-30

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