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WO1996008541A1 - Adsorbent/organic matrix composition using saturated olefin polymers - Google Patents

Adsorbent/organic matrix composition using saturated olefin polymers Download PDF

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Publication number
WO1996008541A1
WO1996008541A1 PCT/US1995/006245 US9506245W WO9608541A1 WO 1996008541 A1 WO1996008541 A1 WO 1996008541A1 US 9506245 W US9506245 W US 9506245W WO 9608541 A1 WO9608541 A1 WO 9608541A1
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WO
WIPO (PCT)
Prior art keywords
composition
adsorbent
weight
parts
olefin polymer
Prior art date
Application number
PCT/US1995/006245
Other languages
French (fr)
Inventor
David A. Gibbs
James Neil Pryor
Victor M. Deeb
Original Assignee
W.R. Grace & Co.-Conn.
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 W.R. Grace & Co.-Conn. filed Critical W.R. Grace & Co.-Conn.
Priority to AU26402/95A priority Critical patent/AU2640295A/en
Publication of WO1996008541A1 publication Critical patent/WO1996008541A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/28—Selection of materials for use as drying agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/677—Evacuating or filling the gap between the panes ; Equilibration of inside and outside pressure; Preventing condensation in the gap between the panes; Cleaning the gap between the panes

Definitions

  • Inorganic adsorbent materials such as molecular sieves, zeolites, etc.
  • Zeolites such as zeolites A and X are widely used in desiccating and gas treatment applications.
  • the adsorbent material is used in the form of a free flowing particulate (e.g. beads) which is allowed to contact the fluid to be treated.
  • the adsorbent may be embedded in a rigid monolithic structure such as a honeycomb.
  • these forms of the adsorbent cannot be used practically.
  • the adsorbent material is loaded into an organic matrix which is then adhered to the spacer.
  • the invention provides improved adsorbent/organic matrix adhesive compositions.
  • the compositions are especially suitable for adherence to metal substrates such as window spacers.
  • the invention encompasses compositions comprising an organic adhesive matrix component and an adsorbent component wherein the organic matrix comprises a saturated olefin polymer.
  • the olefin polymer is preferably a copolymer or terpolymer formed entirely from olefin monomers. Most preferably, the olefin polymer is an ethylene-butene-propylene terpolymer.
  • the organic matrix may also contain other components such as tackifiers.
  • the invention encompasses adsorbent/organic matrix compositions using saturated olefin polymers wherein the adsorbent component comprises a first adsorbent adapted to primarily remove water vapor and a second adsorbent adapted to primarily remove organic volatile components.
  • compositions are preferably suitable for use in insulating glass window spacer applications.
  • Figure 1 shows a plot of viscosity vs. applied shear rate for the composition of the example.
  • Figure 2 shows a plot of water adsorption vs. time for the composition of the example.
  • compositions of the invention generally comprise an organic matrix component and an adsorbent component.
  • the invention encompasses adsorbent/organic matrix adhesive compositions wherein the primary component of the organic matrix is an olefin terpolymer. These compositions are especially suitable for use in window spacer applications.
  • the organic matrix of the invention may be any suitable adhesive saturated olefin polymer suitable for use as a hot melt adhesive.
  • the olefin polymer is preferably a copolymer or terpolymer formed entirely from olefin monomers.
  • the olefin polymer preferably has a Brookfield viscosity (@ 190°C - ASTM D 3236) of about 3000-4000 cP (3.0-4.0 Pa-sec), more preferably about
  • the olefin polymer is an ethylene-butene-propylene terpolymer such as EASTOFLEX T1035 sold by Eastman Chemical Co.
  • the organic matrix also preferably contains a tackifier.
  • a preferred tackifier is polyisobutylene.
  • the preferred polyisobutylene tackifier has a molecular weight of about 8000-15000, more preferably about 10000- 12000.
  • the most preferred polyisobutylenes are those sold by Exxon Chemical Co. under the VISTANEX trademark, such as VISTANEX LM-MH.
  • the organic matrix also preferably contains an anti-oxidant. Any commercially available antioxidant may be used as long as it does not adversely impact the performance of the composition to any significant extent.
  • a preferred anti-oxidant tetrakis[methylene-3 (3' ,5'-di-tert.butyl-4*-hydroxy- phenyl)propionate]methane is sold by Ciba-Geigy Co. as IRGANOX 1010.
  • the proportions of the materials contained in the organic matrix can be varied depending on the nature of the end use.
  • the matrix comprises about 38-45 parts by weight of the olefin terpolymer, more preferably about 40- ⁇ 2 parts by weight, and about 2-6 parts by weight of tackifier, more preferably about 3-5 parts by weight.
  • the amount of anti-oxidant in the matrix is preferably about 0.1-0.5 parts by weight, more preferably about 0.3 parts.
  • the adsorbent component may comprise any suitable adsorbent or combination of adsorbents.
  • the adsorbent component comprises at least two different adsorbents wherein the first adsorbent is adapted to primarily remove water vapor and the second adsorbent is adapted to primarily remove organic volatile components.
  • Preferred water-removing adsorbent is zeolite 3A, however other zeolites having similar or somewhat smaller pore diameter may be used.
  • the organic-removing zeolite preferably has a pore diameter large enough to adsorb cyclic organic compounds such as benzene or toluene.
  • Preferred organic-removing adsorbents are zeolites which have an average pore diameter of at least about 7A.
  • Zeolite Na-X (zeolite 13X) is generally preferred.
  • the adsorbent component preferably comprises about 37-52 parts by weight of water-removing adsorbent, more preferably about 42-48 parts by weight, and about 3-7 parts by weight of the organic-removing adsorbent, more preferably about 4-5 parts by weight.
  • the overall composition preferably comprises about 40-55 wt.% of adsorbent component, more preferably about 45-50 wt.%.
  • the composition may contain other known expedients such as coloring agents, dispersants, etc. as long as they do not adversely affect the performance of the composition to a significant extent.
  • compositions of the invention may be formed by any conventional blending method.
  • the ingredients of the organic matrix are combined together before addition of the adsorbent component.
  • the mixing is preferably conducted with heating (about 180-310°F) to reduce the viscosity of the olefin polymer.
  • the adsorbent components are preferably thermally activated using conditions known in the art before they are combined with the organic matrix. Where multiple adsorbents are used, preferably the adsorbents are physically blended with each other before addition to the heated matrix. Once the heated composition is formed, it can be immediately applied to the desired substrate or it can be cooled and stored for later application to a substrate by conventional hot melt techniques.
  • EASTMAN T105 451 lbs. of ethylene-butene-propylene terpolymer (EASTMAN T1035) were combined with 45 lbs. of polyisobutylene (VISTANEX LM-MH) , 3.3 lbs. of antioxidant (IRGANOX 1010) and 49.5 lbs. of medium gray coloring agent (Ti ⁇ 2 and carbon black) sold by Standridge Color

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Adsorbent/organic matrix adhesive compositions wherein the organic matrix comprises a satured olefin polymer are suitable for adherence to metal substrates such as window spacers. The olefin polymer is preferably a copolymer or terpolymer formed entirely from olefin monomers, most preferably an ethylene-butene-propylene terpolymer. The organic matrix may also contain other components such as tackifiers.

Description

ADSORBENT/ORGA ΪC MATRIX COMPOSITION USING SATURATED OLEFIN POLYMERS
Background of the Invention
Inorganic adsorbent materials, such as molecular sieves, zeolites, etc., have long been used to remove undesired constituents from (gaseous and/or liquid) fluids. Zeolites such as zeolites A and X are widely used in desiccating and gas treatment applications.
In many instances, the adsorbent material is used in the form of a free flowing particulate (e.g. beads) which is allowed to contact the fluid to be treated. In other instances, the adsorbent may be embedded in a rigid monolithic structure such as a honeycomb. For many applications, these forms of the adsorbent cannot be used practically. For example, in the recently developed window spacer structures disclosed in U.S. Patents 5,177,916 and 5,255,481, the adsorbent material is loaded into an organic matrix which is then adhered to the spacer.
In such window spacer applications, there are many demands placed on the adsorbent/organic matrix system used. The system must be easy to apply to the spacer and mechanically stable through the fabrication and service life of the window. Additionally, the system must be able to effectively perform its adsorbing function without degradation on exposure to temperature changes, sunlight, etc. While some systems have been proposed for the type of spacer application mentioned above, there remains a need for more effective and reliable adsorbent/organic matrix systems. flιιιrnιmτ-γ oψ the Invention
The invention provides improved adsorbent/organic matrix adhesive compositions. The compositions are especially suitable for adherence to metal substrates such as window spacers.
In one aspect, the invention encompasses compositions comprising an organic adhesive matrix component and an adsorbent component wherein the organic matrix comprises a saturated olefin polymer. The olefin polymer is preferably a copolymer or terpolymer formed entirely from olefin monomers. Most preferably, the olefin polymer is an ethylene-butene-propylene terpolymer. The organic matrix may also contain other components such as tackifiers. In another aspect, the invention encompasses adsorbent/organic matrix compositions using saturated olefin polymers wherein the adsorbent component comprises a first adsorbent adapted to primarily remove water vapor and a second adsorbent adapted to primarily remove organic volatile components.
The compositions are preferably suitable for use in insulating glass window spacer applications. These and other aspects of the invention will be described in further detail below.
Brief Description of the Drawings
Figure 1 shows a plot of viscosity vs. applied shear rate for the composition of the example.
Figure 2 shows a plot of water adsorption vs. time for the composition of the example. Detailed Description of the Invention
The compositions of the invention generally comprise an organic matrix component and an adsorbent component. The invention encompasses adsorbent/organic matrix adhesive compositions wherein the primary component of the organic matrix is an olefin terpolymer. These compositions are especially suitable for use in window spacer applications.
The organic matrix of the invention may be any suitable adhesive saturated olefin polymer suitable for use as a hot melt adhesive. The olefin polymer is preferably a copolymer or terpolymer formed entirely from olefin monomers. The olefin polymer preferably has a Brookfield viscosity (@ 190°C - ASTM D 3236) of about 3000-4000 cP (3.0-4.0 Pa-sec), more preferably about
3000-3500 cP. Most preferably, the olefin polymer is an ethylene-butene-propylene terpolymer such as EASTOFLEX T1035 sold by Eastman Chemical Co.
The organic matrix also preferably contains a tackifier. A preferred tackifier is polyisobutylene.
The preferred polyisobutylene tackifier has a molecular weight of about 8000-15000, more preferably about 10000- 12000. The most preferred polyisobutylenes are those sold by Exxon Chemical Co. under the VISTANEX trademark, such as VISTANEX LM-MH. The organic matrix also preferably contains an anti-oxidant. Any commercially available antioxidant may be used as long as it does not adversely impact the performance of the composition to any significant extent. A preferred anti-oxidant tetrakis[methylene-3 (3' ,5'-di-tert.butyl-4*-hydroxy- phenyl)propionate]methane is sold by Ciba-Geigy Co. as IRGANOX 1010.
To some extent, the proportions of the materials contained in the organic matrix can be varied depending on the nature of the end use. Preferably, the matrix comprises about 38-45 parts by weight of the olefin terpolymer, more preferably about 40-^2 parts by weight, and about 2-6 parts by weight of tackifier, more preferably about 3-5 parts by weight. The amount of anti-oxidant in the matrix is preferably about 0.1-0.5 parts by weight, more preferably about 0.3 parts.
The adsorbent component may comprise any suitable adsorbent or combination of adsorbents. Preferably, the adsorbent component comprises at least two different adsorbents wherein the first adsorbent is adapted to primarily remove water vapor and the second adsorbent is adapted to primarily remove organic volatile components.
Preferred water-removing adsorbent is zeolite 3A, however other zeolites having similar or somewhat smaller pore diameter may be used. The organic-removing zeolite preferably has a pore diameter large enough to adsorb cyclic organic compounds such as benzene or toluene. Preferred organic-removing adsorbents are zeolites which have an average pore diameter of at least about 7A. Zeolite Na-X (zeolite 13X) is generally preferred.
The adsorbent component preferably comprises about 37-52 parts by weight of water-removing adsorbent, more preferably about 42-48 parts by weight, and about 3-7 parts by weight of the organic-removing adsorbent, more preferably about 4-5 parts by weight.
The overall composition preferably comprises about 40-55 wt.% of adsorbent component, more preferably about 45-50 wt.%. The composition may contain other known expedients such as coloring agents, dispersants, etc. as long as they do not adversely affect the performance of the composition to a significant extent.
The compositions of the invention may be formed by any conventional blending method. Preferably, the ingredients of the organic matrix are combined together before addition of the adsorbent component. Since the olefin polymers of the invention possess hot melt characteristics, the mixing is preferably conducted with heating (about 180-310°F) to reduce the viscosity of the olefin polymer. The adsorbent components are preferably thermally activated using conditions known in the art before they are combined with the organic matrix. Where multiple adsorbents are used, preferably the adsorbents are physically blended with each other before addition to the heated matrix. Once the heated composition is formed, it can be immediately applied to the desired substrate or it can be cooled and stored for later application to a substrate by conventional hot melt techniques.
Example
451 lbs. of ethylene-butene-propylene terpolymer (EASTMAN T1035) were combined with 45 lbs. of polyisobutylene (VISTANEX LM-MH) , 3.3 lbs. of antioxidant (IRGANOX 1010) and 49.5 lbs. of medium gray coloring agent (Tiθ2 and carbon black) sold by Standridge Color
Corp. in a Nauta mixer heated with an oil jacket to about 180°F. The initial mixing resulted in a rise in temperature for the mixture to about 250°F. 495 lbs. of zeolite 3A (Grace Davison) and 55 lbs. of zeolite 13X (Grace Davison) were activated and added to the mixer. During the subsequent mixing, heat was generated by the mixing action such that the temperature of the mixture reached a maximum of about 310°F. The total mixing time was about 8 hours. The resulting composition had excellent adsorptive, rheological, and mechanical properties. The water adsorption of the composition is shown in Figure 1. The viscosity of the composition as a function of shear rate is shown in Figure 2.

Claims

- 6 -
WHAT IS CLAIMED IS;
1. A adsorbent adhesive composition comprising an organic adhesive matrix component and an adsorbent component wherein said organic matrix comprises a saturated olefin polymer.
2. The composition of Claim 1 wherein said matrix further comprises a tackifier.
3. The composition of Claim 1 wherein said adsorbent component comprises α first adsorbent adapted to primarily adsorb water and a second adsorbent adapted to primarily adsorb organic volatiles.
4. The composition of Claim 2 wherein said tackifier comprises polyisobutylene.
5. The composition of Claim 3 wherein at least a portion said first adsorbent is zeolite 3A.
6. The composition of Claim 3 wherein at least a portion of said second adsorbent is zeolite 13X.
7. The composition of Claim 1 wherein said olefin polymer is a copolymer or terpolymer.
8. The composition of Claim 7 wherein said copolymer or terpolymer is formed entirely from olefin monomers.
9. The composition of Claim 8 wherein said olefin polymer is an ethylene-butene-propylene terpolymer. 10. The composition of Claim 1 wherein said composition comprises about 40-55 wt.% of said adsorbent component.
li. The composition of Claim 1 wherein said matrix also comprises an anti-oxidant.
12. The composition of Claim 3 wherein said desiccant component comprises about 37-52 parts by weight of said first adsorbent and 3-7 parts by weight of said second adsorbent.
13. The composition of Claim 12 wherein said desiccant component comprises about 42-48 parts by weight of said first adsorbent and 4-5 parts by weight of said second adsorbent.
14. The composition of Claim 2 wherein said organic matrix comprises about 38-45 parts by weight of said olefin polymer and about 2-6 parts by weight of tackifier.
15. The composition of Claim 14 wherein said organic matrix comprises about 40-42 parts by weight of said olefin polymer and about 3-5 parts by weight of tackifier.
16. The composition of Claim 1 wherein said olefin polymer has a Brookfield viscosity 190°C of about 3000- 4000 cP.
17. The composition of Claim 1 wherein said composition further comprises a coloring agent. 18. A coated metal substrate suitaole for use as a window spacer wherein the substrate is coated with a composition comprising an adsorbent component in an organic matrix which contains a saturated olefin polymer,
PCT/US1995/006245 1994-09-13 1995-05-15 Adsorbent/organic matrix composition using saturated olefin polymers WO1996008541A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU26402/95A AU2640295A (en) 1994-09-13 1995-05-15 Adsorbent/organic matrix composition using saturated olefin polymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30431294A 1994-09-13 1994-09-13
US08/304,312 1994-09-13

Publications (1)

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WO1996008541A1 true WO1996008541A1 (en) 1996-03-21

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996037278A1 (en) * 1995-05-26 1996-11-28 W.R. Grace & Co.-Conn. Compositions using high-potassium zeolite a
WO1998044063A1 (en) * 1997-04-02 1998-10-08 H.B. Fuller Licensing & Financing, Inc. Pumpable desiccated mastic
US6180708B1 (en) 1996-06-28 2001-01-30 W. R. Grace & Co.-Conn. Thermoplastic adsorbent compositions containing wax and insulating glass units containing such compositions

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* Cited by examiner, † Cited by third party
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DE19913761B4 (en) * 1999-03-26 2005-02-10 Lts Lohmann Therapie-Systeme Ag Drying apparatus and method for its production and its use
CN105561744B (en) * 2016-01-26 2018-01-23 张云 Long-acting deoxidation combination drying agent prescription sheet material and its manufacture method

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WO1989006669A1 (en) * 1988-01-21 1989-07-27 Uniroyal Plastics Company, Inc. Adhesive for bonding cured epdm rubber

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IT1157273B (en) * 1982-05-07 1987-02-11 Anic Spa THERMOPLASTIC COMPOSITIONS BASED ON NON-POLAR ORGANIC POLYMERS AND ZEOLITES IN ACID FORM, WITH TENACE ADHESION TO METALS AND COMPOSITE OBJECTS OBTAINABLE THROUGH THE SAME
JPS5925829A (en) * 1982-08-05 1984-02-09 Chisso Corp Polyolefinic resin composition
IT1214578B (en) * 1986-12-11 1990-01-18 Eniricerche Spa POLIOLEFINE. METAL SURFACES COATING PROCEDURE WITH
US5177916A (en) * 1990-09-04 1993-01-12 Ppg Industries, Inc. Spacer and spacer frame for an insulating glazing unit and method of making same
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WO1989006669A1 (en) * 1988-01-21 1989-07-27 Uniroyal Plastics Company, Inc. Adhesive for bonding cured epdm rubber

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6112477A (en) * 1993-03-15 2000-09-05 H. B. Fuller Licensing & Financing Inc. Pumpable desiccated mastic
WO1996037278A1 (en) * 1995-05-26 1996-11-28 W.R. Grace & Co.-Conn. Compositions using high-potassium zeolite a
US5773380A (en) * 1995-05-26 1998-06-30 W. R. Grace & Co.-Conn. Compositions using high-potassium zeolite A
US6180708B1 (en) 1996-06-28 2001-01-30 W. R. Grace & Co.-Conn. Thermoplastic adsorbent compositions containing wax and insulating glass units containing such compositions
US6777481B2 (en) 1996-06-28 2004-08-17 W. R. Grace & Co.-Conn. Thermoplastic adsorbent compositions containing wax and insulating glass units containing such compositions
WO1998044063A1 (en) * 1997-04-02 1998-10-08 H.B. Fuller Licensing & Financing, Inc. Pumpable desiccated mastic

Also Published As

Publication number Publication date
AU2640295A (en) 1996-03-29
DE19513627A1 (en) 1996-03-14

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