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WO1995018183A1 - Resines epoxy compatibles avec des agents de durcissement polyamine - Google Patents

Resines epoxy compatibles avec des agents de durcissement polyamine Download PDF

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Publication number
WO1995018183A1
WO1995018183A1 PCT/US1994/014550 US9414550W WO9518183A1 WO 1995018183 A1 WO1995018183 A1 WO 1995018183A1 US 9414550 W US9414550 W US 9414550W WO 9518183 A1 WO9518183 A1 WO 9518183A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
epoxy resin
epoxy
weight
meth
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.)
Ceased
Application number
PCT/US1994/014550
Other languages
English (en)
Inventor
A. Frank Leo
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.)
Henkel Corp
Original Assignee
Henkel Corp
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 Henkel Corp filed Critical Henkel Corp
Publication of WO1995018183A1 publication Critical patent/WO1995018183A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/147—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • This invention relates to epoxy resins and their uses. More particularly, the invention relates to epoxy resin compositions compatible with polyamine curing agents.
  • U.S. 4,051,195 relates to blends of an epoxide resin and a poiy(meth)acrylate ester, which cure rapidly with aliphatic polyamine curing agents even at low temperatures.
  • Such compositions can be employed as coatings, adhesives, castings, moldings and the like at high solids contents, including 100% solids content (so-called sêtless compositions).
  • compositions comprise an important advance in the art, since the cured compositions can be formulated to range from flexible to very hard, the latter type tend to be brittle and to have low impact resistance, which are serious disadvantages for their use as coatings, moldings, castings, and the like.
  • U.S.4,547,562 discloses sreteless polymeric compositions suitable for coatings and moldings formed by the addition reaction product of a first component comprising mono, di or poly amines, amine-terminated structures or an adduct of mono, di or polyamines with mono, di or polyfunctional acrylates or epoxides; and the second component comprising mono, di or poly acrylates, mixtures of mono, di or poly acrylates, or a mixture of mono, di or poly acrylates and mono, di or polyfunctional epoxides and/or glycidyl esters of acrylic acid or methacrylic acid.
  • compositions when cured can be used as adhesives, varnishes, lacquers, paints, or sealants.
  • the coatings tend to be brittle, with low impact resistance.
  • the two component epoxy resin system of the invention comprises A) a liquid epoxy resin component containing
  • the epoxy resin (component A) a) above) includes those epoxy resins having two or more 1,2-epoxy groups per molecule.
  • the epoxy resins include those set forth in U.S.4,051,195, which patent is expressly incorporated herein by reference. Such epoxy resins are liquid, saturated or unsaturated, aliphatic, cycloaliphatic or heterocyclic and can be either monomeric or polymeric.
  • Preferred epoxy resins for use herein are the epoxy novolac resins of formula I
  • R H or CH 3
  • n 0 to 4.
  • epoxy novolac resins of formula I are usually mixtures of ortho, meta and para isomers. Also preferred are epoxy resins of formula II
  • R H or CH 3
  • the multifunctional (meth)acrylate esters (component A)b) above) useful in the practice of the invention include those esters set forth in U.S. 4,051,195, which is expressly incorporated herein by reference. These multifunctional (meth) acrylate esters should have a viscosity not greater than 5000 cps, and preferably not greater than 500 cps.
  • Preferred esters are diols or triols, optionally ethoxylated and/or propoxylated with from 1 to 8 EO and/or PO groups, wherein all hydroxyl groups are in the form of acrylate esters, e.g. trimetha ⁇ ol triacrylate. Most preferred are esters of the following formulae:
  • x is an integer of from 2-6
  • y is an integer of from 1 -6 and R 1 is H or CH 3 .
  • Examples of compounds within the above formulae include 1,3-propanediol diacrylate, 1,6-hexanediol diacrylate, and tripropyleneglycol diacrylate.
  • multifunctional (meth) acrylate esters having a viscosity above 500 cps are present, they are preferably present in relatively small quantities, e.g. from 0.1 to 25%, based on the total weight of (meth)acrylate ester.
  • Such higher viscosity esters are e.g. sugar polyacrylates, and in fact their presence may be useful in increasing the crosslink density of the cured epoxy.
  • multifunctional methacrylate esters are within the scope of the invention, these esters are usually somewhat less desirable for use herein than the corresponding multifunctional acrylate esters due to their somewhat slower rates of reaction and more limited miscibility with the epoxy resins.
  • the multifunctional (meth)acryiate esters are in the form of esters of (meth)acrylic acid, e.g. in the case of a triol or higher polyol having one or more free hydroxyl groups
  • the nonesterified hydroxyl groups can be present as such or in the form of C 1 -C 3 alkoxy groups, preferably methoxy. It is however usually preferred to esterify all hydroxyl groups with (meth)acrylic acid.
  • R is H or CH 3
  • R 1 is H or CH 3 , n is an integer of from 0-6,
  • n is an integer of from 0-6, and
  • n + m 1-6, preferably 2-6,
  • component A)b) above when used as component A)b) above, greatly improves the impact resistance and flexibility of the cured compositions, even without the presence of any polyurethane di(meth)acrylate (component A)c) above).
  • the polyurethane poly(meth) acrylates (component A)c) above) contain from 2 to 6 (meth) acrylate groups, are aliphatic or aromatic polyurethane derivatives, are highly viscous or solid, having a weight average molecular weight in the range of from 1200 to 5000, preferably 1200 to 1800. They are employed in amounts ranging from 0.1 to 25%, preferably 1 to 15%,and more preferably 1 to 10% by weight, based on the combined weight of components A)a) and A)b).
  • polyurethane diacrylates are usually prepared by reacting a diisocyanate with hydroxyethyl acrylate in a 1 :1 molar ratio, so that the resulting adduct contains a free isocyanate group, and then reacting two moles of this adduct with one mole of a dihydroxy polyether or polyester.
  • the hardener component (component B)) of the present two component epoxy resin systems are aliphatic polyamines such as polyalkyiene polyamines, e.g. ethylenediamine (H 2 NCH 2 CH 2 NH 2 ) dimethylethylene diamine (CH 3 NHCH 2 CH 2 NHCH 3 ), diethylenetriamine (H 2 NCH 2 CH 2 NHCH 2 CH 2 NH 2 ), tetramethylene diamine (H 2 NCH 2 CH 2 CH 2 CH 2 NH 2 ), triethylenetetramine (H 2 NCH 2 CH 2 NHCH 2 CH 2 NHCH 2 CH 2 NH 2 ), hexamethylene diamine (H 2 N(CH 2 ) 6 NH 2 ), etc.
  • polyalkyiene polyamines e.g. ethylenediamine (H 2 NCH 2 CH 2 NH 2 ) dimethylethylene diamine (CH 3 NHCH 2 CH 2 NHCH 3 ), diethylenetriamine (H 2 NCH 2 CH 2 NHCH 2 CH 2
  • polyamide curing agents i.e. amidoamines obtained by reacting a polyamine such as the above with straight or branched chain saturated aliphatic polycarboxylic acids, e.g. having from 2-50 carbon atoms in the alkylene groups, in which each carboxylic acid group has been reacted with a molecule of a polyamine.
  • the resulting polyamides must contain at least two amine groups that are primary and/or secondary in nature.
  • Preferred polyamide curing agents are the reaction products of one mol of a C 36 fatty diacid from the dimerization of a C 18 unsaturated fatty acid with two mols of diethylenetriamine or triethylenetetramine.
  • polyamines containing epoxy groups can be employed herein.
  • the hardener component can optionally contain quantities of other ingredients, e.g. from 0.001 to 65% by weight, based on the weight of polyamine curing agent, of ingredients such as accelerators, fillers, reinforcing agents, dyes, pigments and other additives.
  • the percentage ratio by weight of component A)a) to component A)b) is from 85:15 to 20:80.
  • the particular ratio selected within the above range is not critical and will depend on the particular components chosen and the properties desired for the cured epoxy product.
  • Components A and B are used in an equivalent ratio of epoxy groups plus acrylate groups in the epoxy resin component to amine hydrogen atoms in the hardener component of from 0.85:1 to 1:1.15, preferably from 0.95:1 to 1:1.05, and more preferably 1:1.
  • the two component epoxy resin systems of the invention are applied by mixing together the epoxy resin component and the hardener component in the absence of solvents and applying the mixture at a temperature of from 0° to 150°F, preferably from 40° to 110oF, and more preferably from 40° to 95oF.
  • solvents thereto such as hydrocarbons, ethers, alcohols, esters, ketones, etc.
  • solvents are highly undesirable, acting to reduce the solids contents, presenting environmental and safety problems, and causing a reduction in physical properties, e.g. in thick coatings of 20-1000 mils, solvents will be trapped in the coatings, resulting in cheesey films.
  • the two component epoxy resin system can be used as an adhesive system to bond two like or different substrates together as with other epoxy adhesives; as tough resilient nonbrittle coatings having high impact resistance for hard surfaces, including coatings for floors; as casting, molding and potting compositions; and as encapsulating compositions.
  • the epoxy system can be used immediately after mixing due to its low viscosity, even at a relatively high solids content, and its increased reactivity even at relatively low cure temperatures. Short cure times are also achieved.
  • the cured mixtures exhibit excellent flexibility, impact resistance, and good chemical resistance.
  • thick coatings containing 100% solids content e.g. from 0.5 to 1 inch thick, can be readily applied to a substrate.
  • the epoxy systems of the invention can also be used as paint compositions, when mixed with paint pigments.
  • the paint coatings resulting from their use are unusually tough, adhesive and chemically resistant.
  • a two component epoxy resin system is prepared from the following ingredients:
  • DER 331 is the diglycidyl ether of bisphenol A.
  • PHOTOMER® 6022 is an aromatic polyurethane containing six acrylate groups, a viscosity of from 500-800 poises, and a weight average molecular weight of 800.
  • PHOTOMER® 4127 is a neopentylglycol- 2PO- diacrylate.
  • a two component epoxy resin system is prepared from the following ingredients:
  • VERSAMINE ® A-50 is an epoxy derivative of diethylenetriamine.
  • a two component epoxy resin system is prepared from the following ingredients:
  • PHOTOMER® 4025 is bisphenol A-8EO- diacrylate.
  • a two component epoxy resin system is prepared from the following ingredients:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

L'incorporation de poly(méth)acrylate(s) de polyuréthane dans une composition comprenant une(des) résine(s) époxy, un(des) ester(s) de (méth)acrylate multifonctionnel(s) d'un polyol qui forme un ester avec de l'acide (méth)acrylique, et un agent de durcissement polyamine, permet d'obtenir une(des) résine(s) époxy durcies, dures et non fragiles, qui ont une résistance élevée aux chocs et s'utilise(nt) comme adhésif ou comme revêtement.
PCT/US1994/014550 1993-12-29 1994-12-23 Resines epoxy compatibles avec des agents de durcissement polyamine Ceased WO1995018183A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17496593A 1993-12-29 1993-12-29
US08/174,965 1993-12-29

Publications (1)

Publication Number Publication Date
WO1995018183A1 true WO1995018183A1 (fr) 1995-07-06

Family

ID=22638259

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/014550 Ceased WO1995018183A1 (fr) 1993-12-29 1994-12-23 Resines epoxy compatibles avec des agents de durcissement polyamine

Country Status (1)

Country Link
WO (1) WO1995018183A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0675144A3 (fr) * 1994-03-16 1996-04-03 Air Prod & Chem Résines époxydes flexibilisées contenant des polyamides secondaires-N-méthylées.
US6911109B2 (en) * 2000-12-11 2005-06-28 Henkel Corporation Two-part, room temperature curable epoxy resin/ (meth)acrylate compositions and process for using same to bond substrates
US7071263B2 (en) 2003-05-19 2006-07-04 3M Innovative Properties Company Epoxy adhesives and bonded substrates
US9207373B2 (en) 2007-04-10 2015-12-08 Stoncor Group, Inc. Methods for fabrication and highway marking usage of agglomerated retroreflective beads
WO2018226710A1 (fr) * 2017-06-09 2018-12-13 Hexion Inc. Systèmes de résine époxy pour composites
EP4520774A1 (fr) * 2023-09-11 2025-03-12 Sika Technology AG Utilisation d'acrylates dans des systèmes époxy

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6157909A (ja) * 1984-08-29 1986-03-25 Showa Electric Wire & Cable Co Ltd 光部品の固定方法
JPS63118388A (ja) * 1986-11-06 1988-05-23 Aica Kogyo Co Ltd 軟質塩ビ用接着剤
US4755571A (en) * 1984-04-28 1988-07-05 Ciba-Geigy Corporation Curable compositions
US5026794A (en) * 1989-05-23 1991-06-25 Polysar Limited Adducts of an hydroxy-free acrylate resin and an epoxy resin
US5098780A (en) * 1990-12-13 1992-03-24 Sandoz Ltd. Corrosion resistant linings for concrete surfaces
JPH04149444A (ja) * 1990-10-12 1992-05-22 Ryoden Kasei Co Ltd ２液混合型硬化性樹脂組成物
JPH04149443A (ja) * 1990-10-12 1992-05-22 Ryoden Kasei Co Ltd ２液混合型硬化性樹脂組成物
US5198524A (en) * 1991-04-22 1993-03-30 W.R. Grace & Co.-Conn. Moisture-curing acrylate/epoxy hybrid adhesives
US5202365A (en) * 1991-06-13 1993-04-13 Reactive Industries, Inc. Packaged adhesive

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4755571A (en) * 1984-04-28 1988-07-05 Ciba-Geigy Corporation Curable compositions
JPS6157909A (ja) * 1984-08-29 1986-03-25 Showa Electric Wire & Cable Co Ltd 光部品の固定方法
JPS63118388A (ja) * 1986-11-06 1988-05-23 Aica Kogyo Co Ltd 軟質塩ビ用接着剤
US5026794A (en) * 1989-05-23 1991-06-25 Polysar Limited Adducts of an hydroxy-free acrylate resin and an epoxy resin
JPH04149444A (ja) * 1990-10-12 1992-05-22 Ryoden Kasei Co Ltd ２液混合型硬化性樹脂組成物
JPH04149443A (ja) * 1990-10-12 1992-05-22 Ryoden Kasei Co Ltd ２液混合型硬化性樹脂組成物
US5098780A (en) * 1990-12-13 1992-03-24 Sandoz Ltd. Corrosion resistant linings for concrete surfaces
US5198524A (en) * 1991-04-22 1993-03-30 W.R. Grace & Co.-Conn. Moisture-curing acrylate/epoxy hybrid adhesives
US5202365A (en) * 1991-06-13 1993-04-13 Reactive Industries, Inc. Packaged adhesive

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0675144A3 (fr) * 1994-03-16 1996-04-03 Air Prod & Chem Résines époxydes flexibilisées contenant des polyamides secondaires-N-méthylées.
US6911109B2 (en) * 2000-12-11 2005-06-28 Henkel Corporation Two-part, room temperature curable epoxy resin/ (meth)acrylate compositions and process for using same to bond substrates
US7071263B2 (en) 2003-05-19 2006-07-04 3M Innovative Properties Company Epoxy adhesives and bonded substrates
US9207373B2 (en) 2007-04-10 2015-12-08 Stoncor Group, Inc. Methods for fabrication and highway marking usage of agglomerated retroreflective beads
WO2018226710A1 (fr) * 2017-06-09 2018-12-13 Hexion Inc. Systèmes de résine époxy pour composites
US11292871B2 (en) 2017-06-09 2022-04-05 Hexion Inc. Epoxy resin systems for composites
EP4520774A1 (fr) * 2023-09-11 2025-03-12 Sika Technology AG Utilisation d'acrylates dans des systèmes époxy
WO2025056521A1 (fr) 2023-09-11 2025-03-20 Sika Technology Ag Utilisation d'acrylates dans des systèmes époxy

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