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GB2077741A - Non-flammable polyurethane adhesive - Google Patents

Non-flammable polyurethane adhesive Download PDF

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Publication number
GB2077741A
GB2077741A GB8019188A GB8019188A GB2077741A GB 2077741 A GB2077741 A GB 2077741A GB 8019188 A GB8019188 A GB 8019188A GB 8019188 A GB8019188 A GB 8019188A GB 2077741 A GB2077741 A GB 2077741A
Authority
GB
United Kingdom
Prior art keywords
adhesive
ester
isocyanate
polyurethane
tris
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
GB8019188A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AIRBORNE IND Ltd
Original Assignee
AIRBORNE IND Ltd
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 AIRBORNE IND Ltd filed Critical AIRBORNE IND Ltd
Priority to GB8019188A priority Critical patent/GB2077741A/en
Publication of GB2077741A publication Critical patent/GB2077741A/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/06Homopolymers or copolymers containing elements other than carbon and hydrogen
    • C08L57/10Homopolymers or copolymers containing elements other than carbon and hydrogen containing oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition 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
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition 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
    • C08L2666/28Non-macromolecular organic substances
    • C08L2666/40Phosphorus-containing compounds

Landscapes

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

Abstract

An adhesive comprises an isocyanate terminated polyurethane or urethane prepolymer and an ester which imparts non-inflammability to the adhesive particularly a tri(2- chloroethyl)ester of phosphoric acid.

Description

SPECIFICATION Non-flarnmable adhesive The present invention relates to adhesives and more particularly to non-flammable adhesives incorporating an isocyanate-terminated polyurethane. The base for polyurethane can be caprolacton, ether or polyester.
The use of isocyanate-terminated polyurethanes and urethane propolymers, as adhesives is known. However, such compounds suffer from the disadvantage that they are inflammable.
According to the present invention there is provided an adhesive, comprising an isocyanateterminated polyurethane or urethane prepolymer and an ester which imparts non-inflammability to the adhesive. The ester is preferably a phosphorus ester such as a phosphoric acid ester, for example phosphoric acid tris-(2 chloroethyl)-ester-tris-(2chloroethyl)-orthophosphoric acid ester.
The adhesive may also include styrene and isobutylene polymers of carboxylated vinyl resins where the carboxyl groups provide points of reactivity for crosslinking with polyurethanes.
Praferred embodiments of the invention will now be described. In a first embodiment the starting material is an isocyanate-terminated urethane prepolymer based on MDI (modified di-isocyanate) and polycaprolactone base.
To produce the adhesive 100 parts by weight of this compound are melted and heated to about 1 800C in an atmosphere of nitrogen. 20 to 30 parts by weight of phosphorus ester are separately heated to the same temperature and then stirred into the prepolymer.
The resulting product may be regarded as nonflammable for most purposes; however prolonged heating about 2000C should be avoided. Although its flashpoint is 2250C its vapours will burn at 2500C only when in constant contact with a naked flame. Regarding its flammability characteristics according to ASTM D 1 962-68 the extent of flame spread is a maximum of 20mm.
The product does not contain any free hydroxyl groups and has good compatibility with other materials. The adhesive is air or preferably moisture curable.
A particular advantage of the adhesive is that it need not contain any solvent, which leads to improved safety. Of course, solvents may be included, depending on the particular characteristics required, and ketones, including Methyl Ethyl Ketone, Acetone, Methylene Chloride and Trichloroethane have all been found to be suitable. An adhesive which is 80% solids may be provided.
The adhesive may be further modified by the incorporation of compatible resins such as styrene and isobutylene copolymers or carboxylated vinyl resins in amounts from 5 to 100 parts by weight.
This increases the green strength of the material and, depending upon the amount of polymers added, the softening point and the open assembly time may be varied. Melting points of between 60"C and 1200C may be obtained and setting times ranging from a few seconds to 2-3 minutes.
Thus the above embodiment provides an adhesive which is non-flammable, has a low melting point, and has a better thermal stability than is normally associated with polyurethane. In addition, it has excellent hydrolysis and ageing resistance. The adhesive may be used to bond a film to another film, to paper or to aluminium foil.
Substrates of polypropylene, polyethylene, polyester or polyvinyl chloride may be bonded to themselves or to aluminium foil, paper or board.
Fabrics may be bonded together or to foam, to provide a soft bond which is mark and dry clean resistant. The adhesive may also be used to bond insulation to the sheet metal lining of refrigerated containers. The adhesive provides flexibility and can withstand arduous service conditions such as water immersion, temperature fluctuation and exposure to many chemicals and plasticizers. It may also be used to provide a non-flammable coating for a surface, such as a ceiling having plastics tiles.
This polymer has no unreacted isocyanate group. The adhesive produced in this way gives excellent adhesion to plasticised PVC, polycarbonate, polyester, expanded polystyrene, polyurethane etc., and produces good flame retarding properties.
The adhesive produced is a hot melt adhesive.
It may be applied by hot roll coaters, by extrusion or by a spatula. In one application the adhesive which is thermoplastic is extended to form a sheet. The sheet is inserted between two articles to be stuck together and the arrangement is heated. Because of its low melting point, the adhesive melts while the articles and laminate remain unaffected to produce a strong bond which provides a non-flame propagating glue-line.
1. An adhesive comprising an isocyanate terminated polyurethane or urethane prepolymer and an ester which imparts non-inflammability to the adhesive.
2. An adhesive as claimed in claim 1, wherein the ester comprises a phosphorous ester.
3. An adhesive as claimed in claim 1 or 2.
wherein the ester comprises a phosperic acid ester.
4. An adhesive as claimed in claim 1, 2 or 3, wherein the ester is phospheric acid tris-(2 chloroethyl)-ester-tris-(2-chloroethyl)orthophosperic acid ester.
5. An adhesive as claimed in any one of claims
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (6)

**WARNING** start of CLMS field may overlap end of DESC **. SPECIFICATION Non-flarnmable adhesive The present invention relates to adhesives and more particularly to non-flammable adhesives incorporating an isocyanate-terminated polyurethane. The base for polyurethane can be caprolacton, ether or polyester. The use of isocyanate-terminated polyurethanes and urethane propolymers, as adhesives is known. However, such compounds suffer from the disadvantage that they are inflammable. According to the present invention there is provided an adhesive, comprising an isocyanateterminated polyurethane or urethane prepolymer and an ester which imparts non-inflammability to the adhesive. The ester is preferably a phosphorus ester such as a phosphoric acid ester, for example phosphoric acid tris-(2 chloroethyl)-ester-tris-(2chloroethyl)-orthophosphoric acid ester. The adhesive may also include styrene and isobutylene polymers of carboxylated vinyl resins where the carboxyl groups provide points of reactivity for crosslinking with polyurethanes. Praferred embodiments of the invention will now be described. In a first embodiment the starting material is an isocyanate-terminated urethane prepolymer based on MDI (modified di-isocyanate) and polycaprolactone base. To produce the adhesive 100 parts by weight of this compound are melted and heated to about 1 800C in an atmosphere of nitrogen. 20 to 30 parts by weight of phosphorus ester are separately heated to the same temperature and then stirred into the prepolymer. The resulting product may be regarded as nonflammable for most purposes; however prolonged heating about 2000C should be avoided. Although its flashpoint is 2250C its vapours will burn at 2500C only when in constant contact with a naked flame. Regarding its flammability characteristics according to ASTM D 1 962-68 the extent of flame spread is a maximum of 20mm. The product does not contain any free hydroxyl groups and has good compatibility with other materials. The adhesive is air or preferably moisture curable. A particular advantage of the adhesive is that it need not contain any solvent, which leads to improved safety. Of course, solvents may be included, depending on the particular characteristics required, and ketones, including Methyl Ethyl Ketone, Acetone, Methylene Chloride and Trichloroethane have all been found to be suitable. An adhesive which is 80% solids may be provided. The adhesive may be further modified by the incorporation of compatible resins such as styrene and isobutylene copolymers or carboxylated vinyl resins in amounts from 5 to 100 parts by weight. This increases the green strength of the material and, depending upon the amount of polymers added, the softening point and the open assembly time may be varied. Melting points of between 60"C and 1200C may be obtained and setting times ranging from a few seconds to 2-3 minutes. Thus the above embodiment provides an adhesive which is non-flammable, has a low melting point, and has a better thermal stability than is normally associated with polyurethane. In addition, it has excellent hydrolysis and ageing resistance. The adhesive may be used to bond a film to another film, to paper or to aluminium foil. Substrates of polypropylene, polyethylene, polyester or polyvinyl chloride may be bonded to themselves or to aluminium foil, paper or board. Fabrics may be bonded together or to foam, to provide a soft bond which is mark and dry clean resistant. The adhesive may also be used to bond insulation to the sheet metal lining of refrigerated containers. The adhesive provides flexibility and can withstand arduous service conditions such as water immersion, temperature fluctuation and exposure to many chemicals and plasticizers. It may also be used to provide a non-flammable coating for a surface, such as a ceiling having plastics tiles. This polymer has no unreacted isocyanate group. The adhesive produced in this way gives excellent adhesion to plasticised PVC, polycarbonate, polyester, expanded polystyrene, polyurethane etc., and produces good flame retarding properties. The adhesive produced is a hot melt adhesive. It may be applied by hot roll coaters, by extrusion or by a spatula. In one application the adhesive which is thermoplastic is extended to form a sheet. The sheet is inserted between two articles to be stuck together and the arrangement is heated. Because of its low melting point, the adhesive melts while the articles and laminate remain unaffected to produce a strong bond which provides a non-flame propagating glue-line. CLAIMS
1. An adhesive comprising an isocyanate terminated polyurethane or urethane prepolymer and an ester which imparts non-inflammability to the adhesive.
2. An adhesive as claimed in claim 1, wherein the ester comprises a phosphorous ester.
3. An adhesive as claimed in claim 1 or 2.
wherein the ester comprises a phosperic acid ester.
4. An adhesive as claimed in claim 1, 2 or 3, wherein the ester is phospheric acid tris-(2 chloroethyl)-ester-tris-(2-chloroethyl)orthophosperic acid ester.
5. An adhesive as claimed in any one of claims 1 to 4, wherein the adhesive includes styrene and isobutylene polymers or carboxylated vinyl resins with the carboxyl groups providing points of activity for cross linking with polyurethanes.
6. An adhesive as claimed in claim 1 and substantially as described herein.
GB8019188A 1980-06-12 1980-06-12 Non-flammable polyurethane adhesive Withdrawn GB2077741A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB8019188A GB2077741A (en) 1980-06-12 1980-06-12 Non-flammable polyurethane adhesive

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8019188A GB2077741A (en) 1980-06-12 1980-06-12 Non-flammable polyurethane adhesive

Publications (1)

Publication Number Publication Date
GB2077741A true GB2077741A (en) 1981-12-23

Family

ID=10513996

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8019188A Withdrawn GB2077741A (en) 1980-06-12 1980-06-12 Non-flammable polyurethane adhesive

Country Status (1)

Country Link
GB (1) GB2077741A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4011060C1 (en) * 1990-04-05 1991-05-08 W. Doellken & Co. Gmbh, 4300 Essen, De Use of polyurethane as hot gluing agent for olefin(s) - includes using compsn. contg. polyether and opt. polyester long chain di:ol(s), di:isocyanate and short chain di:ol(s)
WO1992018577A1 (en) * 1991-04-23 1992-10-29 Morton International S.P.A. Adhesive for bonding a plastic film to a paper support to provide a plastic coating, and particularly suitable for bonding plastic film to sheet paper or cardboard
EP0546771A1 (en) * 1991-12-09 1993-06-16 Gencorp Inc. Two-component urethame adhesive compositions
US5508111A (en) * 1991-03-13 1996-04-16 Gencorp Adhesive composition
US5606003A (en) * 1994-09-01 1997-02-25 Gencorp Inc. Primerless urethane adhesive compositions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4011060C1 (en) * 1990-04-05 1991-05-08 W. Doellken & Co. Gmbh, 4300 Essen, De Use of polyurethane as hot gluing agent for olefin(s) - includes using compsn. contg. polyether and opt. polyester long chain di:ol(s), di:isocyanate and short chain di:ol(s)
US5508111A (en) * 1991-03-13 1996-04-16 Gencorp Adhesive composition
WO1992018577A1 (en) * 1991-04-23 1992-10-29 Morton International S.P.A. Adhesive for bonding a plastic film to a paper support to provide a plastic coating, and particularly suitable for bonding plastic film to sheet paper or cardboard
EP0546771A1 (en) * 1991-12-09 1993-06-16 Gencorp Inc. Two-component urethame adhesive compositions
US5606003A (en) * 1994-09-01 1997-02-25 Gencorp Inc. Primerless urethane adhesive compositions

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Legal Events

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WAP Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1)