Classifications

• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/55—Boron-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
• • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • 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
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether

Definitions

• the present invention relates to curable acrylate or methacrylate compositions. Brief Description of Related Technology
• Organoboranes are often stabilised as amine complexes so that they do not undergo spontaneous autoxidation. These complexes can be activated by acids so that the organoborane can undergo autoxidation when required.
• organoborane: amines can lead to gelation of the composition, which is often a resin-based composition, thus significantly compromising stability over time. Such compositions often do not have a sufficiently long shelf life.
• Low surface energy surfaces such as polyolefins, including polyethylene, polypropylene, polybutene, polyisoprene, and copolymers thereof, are well known to be difficult to bond to each other and to other surfaces using adhesive bonding technology. This is thought to be due to the fact that they have few active bonding sites available at the free surfaces.
• Low energy surfaces typically have surface energy values of less than 45 mJ/m 2 , more typically less than 40 mJ/m 2 , such as less than 35 mJ/m 2 .
• US Patent Application No. 10587872 relates to the use of trialkylborane amines with organometallic aluminium compounds as a method for increasing the stability of borane: amine/methacrylate compositions.
• the organometallic aluminium compounds are however highly water and oxygen sensitive and can produce by-products which deleteriously affect adhesive performance.
• US Patent No. 7,247,596 discloses hydroxyl amines or nitrile oxide as stabilisers for organoborane/methacrylate compositions. Shelf life stability is said to be increased by the use of such stabilisers but this is achieved sometimes with the consequence of reduced bond strength performance.
• US Patent No. 4,999,216 relates to vinyl ether/methacrylate compositions.
• the composition is radically co-polymerised by a photo initiator in the presence of maleate or fumarate monomer.
• Such compositions require surface treatment of low energy surface substrates to allow effective bonding.
• US20070135601 (Huntsman) relates to providing new complexes of organoboranes with amino functional organosilicon compounds which are effective polymerisation initiators for radically polymerisable systems. Huntsman describes use of the organoborane complexes as suitable polymerisation initiators for many polymerisable systems including acrylic or methacrylic monomers and radically polymerisable vinyl ethers.
• US20040242817 also relates to new organoboranes and discloses internally coordinated organoboranes as varying sized rings formed from an unsaturated amine, amidine or guanidine and dialkylhydroborane under hydroboration conditions as well as two-part adhesive coating kits containing radical polymerizable material and the internally coordinated organoborane.
• Kendall describes adhesive or coating embodiments optionally containing a polyvinyl alkyl ether.
• WO200500091 1 (also to Kendall) is concerned with cyclic organnoboranes and compositions comprising same.
• the product sold as Loctite ® 3035 (available from Henkel Corporation, Rocky Hill, CT, USA) is a two-part acrylic adhesive which uses a borane:amine initiator. In a first part it has an initiator and methacrylic esters. In the other part is has methacrylate esters and a co-polymerisable acid.
• a two part polymerisable composition comprising:
• a curable acrylate or methacrylate component a curable acrylate or methacrylate component; an organoborane initiator component;
• compositions of the invention demonstrate good storage stability compared to other compositions comprising acrylate or methacrylate, organoborane and activator.
• Additives may be included in the composition to confer desirable physical properties, for example, polymeric tougheners, silicas and/or other rheology modifiers, for example naturally occurring mineral materials such as zeolites, halloysites, micas, talcs and other particulate material such as wood particulate materials including wood flours, and carbonate salts for example calcium carbonate, sodium carbonate, potassium carbonate, and/or magnesium carbonate, or combinations thereof.
• the vinyl ether component may comprise a vinyl ether molecule, which has at least two vinyl ether groups, for example, a divinyl ether.
• the vinyl ether component may comprise at least one of 1 ,4-Butanediol divinyl ether, diethyleneglycol divinyl ether, and triethyleneglycol divinyl ether.
• Some embodiments of the present invention may comprise a two-part composition comprising:
• a first part comprising an organoborane initiator component and a vinyl ether component
• a second part comprising an activator for the organoborane component.
• the curable acrylate or methacrylate component may be in the same part of the two-part composition as the activator for the organoborane component.
• the organoborane initiator component may comprise a trialkyl borane.
• the organoborane initiator component may comprise a borane:amine complex, for example a trialkylborane:amine complex.
• the organoborane initiator component may be present in an amount from about 0.1 to about 10% weight percentage based on the total weight of the composition, suitably in an amount from about 0.25 to about 5% weight percentage based on the total weight of the composition.
• the activator for the organoborane compound may be selected from the group consisting of Lewis acids, carboxylic acids, phosphoric acids, anhydrides and isocyanates and combinations thereof. [0024] The activator may be present in an amount from about 1 to about 40% weight percentage based on the total weight of the composition, suitably in an amount from about 2 to about 20% weight percentage based on the total weight of the composition.
• Suitable acrylate or methacrylate components include: methyl acrylate, methyl methacrylate, 2-ethylhexyacrylate, 2-ethylhexyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate,_ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n- butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, isooctyl methacrylate, acrylamide, n- methyl acrylamide, lauryl methacrylate and stearyl methacrylate,
• Suitable acrylates or methacrylates are multimeric acrylates and methacrylates as shown below:
• R-i may be H or CrC 20 alkyl, suitably CH 3 and R 2 can link a plurality of monomeric acrylates and/or methacrylates; wherein R 2 may be selected from the group consisting of CrC 2 o alkyl, C 2 -C 2 o alkenyl, C 3 -C 20 cycloalkyl, C 3 -C 20 cycloalkyl optionally having at least one C-C unsaturated bond in the ring, C 5 -C 20 aryl, C 3 -C 20 heteroaryl, urethane, urea, glycol, ether, polyether or glycidyl component, and combinations thereof, optionally substituted one or more times with at least one of hydroxy, amino, halogen, cyano, nitro, Ci-C 5 alkoxy, and/or C 1 -C5 thioalkoxy.
• n can range from 2 to 4 (inclusive of 2 and 4) acrylate units. Examples include: diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1 ,6-hexanediol diacrylate, 1 ,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, tris(2-hydroxyethyl)lsocyanurate triacrylate, tris(2- hydroxyethyl)lso
• Suitable acrylate or methacrylate monomeric units include methyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl acrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1 ,6-hexanediol diacrylate, 1 ,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, or the like.
• the acrylate or methacrylate component can be present in an amount from about 10 to about 95% weight percentage based on the total weight of the composition, desirably from about 20 to about 85% weight percentage based on the total weight of the composition.
• the second part of the composition may comprise a curable component, suitably a maleate, fumarate or maleimide component or combinations thereof.
• a curable component suitably a maleate, fumarate or maleimide component or combinations thereof.
• examples include (but are not limited to) mono-2-(acryloyloxy)ethyl maleate, mono-2- (methacryloyloxy)ethyl maleate, maleic anhydride, maleic acid, toxilic acid, fumaric acid, fumaramide, fumaryl nitrile, fumaryl chloride, fumarate monoethyl ester salts of zinc, calcium and magnesium, 2,5-pyrroledione and 1 ,1 '-(methylenedi-4,1 - phenylene)bismaleimide, or combinations thereof.
• the second part of the composition may also comprise a protic acid compound capable of cationically curing vinyl ether monomers, examples include protic acids such as (but not limited to) acrylic acid, methacrylic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, triflic acid or combinations thereof.
• protic acids such as (but not limited to) acrylic acid, methacrylic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, triflic acid or combinations thereof.
• the second part of the composition may also comprise a Lewis acidic compound capable of cationically curing vinyl ether molecules, examples include (but not limited to) boron trichloride, boron trifluoride or lithium tetrafluoroborate or combinations thereof.
• the maleate, fumarate or maleimide curative component is present in an amount from about 1 to about 20% weight percentage based on the total weight of the composition, suitably in an amount from about 1 .5 to about 10% weight percentage based on the total weight of the composition.
• Some embodiments of the present invention may comprise a toughener component.
• toughener components include synthetic rubbers, such as acrylonitrile/butadiene rubber (NBR rubber), a polyurethane, styrene/butadiene rubber, styrene/butadiene/methacrylate rubber, chloroprene rubber or butadiene rubber, a natural rubber, a styrene thermoplastic elastomer such as styrene/polybutadiene/styrene synthetic rubber, a polyacrylate or polymethacrylate elastomer, a methacrylate/acrylate block co-polymer or an olefin thermoplastic elastomer such as polystyrene/EPDM (an ethylene/propylene/conjugated diene co-polymer) synthetic rubber. Chlorinated and chlorosulfonated polyethylene elastomers can also be used.
• the toughener component can also be a mixture or dispersion of these types of materials.
• the toughener component can be present in an amount from about 5 to about 50% weight percentage based on the total weight of the composition, desirably in an amount from about 10 to about 30% weight percentage based on the total weight of the composition.
• curable acrylate or methacrylate component includes any curable composition based on curing through acrylate or methacrylate functionality and in particular does not exclude combinations of acrylates and/or methacrylates or indeed components having more than one curable functional group.
• organoborane initiator components may be employed.
• Combinations of vinyl ether components may be employed.
• combinations of activators for the organoborane component may be used.
• compositions of the invention show good storage stability yet are still activatable to provide strong and durable bonds.
• compositions of the invention are suitable for use in bonding substrates with low surface energies.
• low energy surfaces typically have surface energy values of less than 45 mJ/m 2 , more typically less than 40 mJ/m 2 , such as less than 35 mJ/m 2 .
• compositions of the invention are suitable for use in bonding low surface energy substrates, either to another low surface energy substrate or to another substrate.
• compositions of the invention can be utilised in bonding polyolefins, including polyethylene, polypropylene, polybutene, polyisoprene, and copolymers thereof.
• the vinyl ether component included in the composition for example in a Part B of the composition may be any vinyl ether, though desirable ones include bis[4- (vinyloxy)butyl] isophthalate (available commercially under the tradename VECTOMER' , such at VECTOMER' M 4010, the chemical structure of which is shown below):
• VECTOMER' M 5015 and VECTOMER' M 4020 may be used as well. Their chemical structures are shown below:
• Additional vinyl ethers that may be used herein and are commercially available from BASF Corporation include Ethyl vinyl ether, n-Butyl vinyl ether, Iso-Butyl vinyl ether, t- Butyl vinyl ether, Cyclohexyl vinyl ether, 1 ,4-Cyclohexanedimethanol divinyl ether, 1 ,4- Cyclohexanedimethanol mono vinyl ether, 2-Ethylhexyl vinyl ether, Dodecyl vinyl ether, Octadecyl vinyl ether, 1 ,4-Butanediol divinyl ether, Diethyleneglycol divinyl ether, Triethyleneglycol divinyl ether and Hydroxybutyl vinyl ether and combinations thereof.
• the vinyl ether component should be included in a Part A of the composition in an amount within the range of from about 0.1 to about 20%, such as to about 0.25 to about 5% by weight based on the total weight of the composition.
• additives may be included in either or both of a Part A or Part B of the composition to influence a variety of performance properties.
• Vinyl ethers/methacrylate compositions of the invention improve adhesion performance on polyolefin, plastic and metal substrates in comparison to organoborane compositions without vinyl ethers.
• the invention relates to a curable composition and desirably one in the form of a two part polymerisable composition.
• a two part composition is referred to as having a "Part A” and a "Part B".
• Part A may include an organoborane initiator, preferably a trialkylborane:amine complex and a vinyl ether monomer (mono- and/or di- functional).
• Methacrylate or acrylate esters both mono- and/or multi-functional
• polymeric tougheners silicas and other rheology modifiers are optionally included.
• Part B contains methacrylate or acrylate esters (both mono- and/or multifunctional) and preferably compounds containing malaeic and/or fumarate functionality.
• An activator for the organoborane compound must also be present and can be chosen (but not limited to) from Lewis acids, carboxylic acids, phosphoric acids, anhydrides and isocyanates. Polymeric tougheners, silicas and other rheology modifiers are optionally included.
• Part A and B were prepared in 500g quantities by mixing the components using a static mixer, mixed with an overhead stirrer.
• the components were then stored separately in a two part cartridge, which can dispense the parts and allow for mixing, for example through a static mixer, before application to a substrate.
• the components can be mixed in ratios from 1 :1 to 10:1.
• Parts A and B were mixed and dispensed through a cartridge fitted with a static mixer and applied to one lap shear covering the area up to 0.5" inches 2 (12.7 mm 2 ) which was then joined to another and clamped for 24h at room temperature.
• Tensile bond strengths were determined using the following test method: the test method was based on ASTM D 1002-05. The lap shears measured 1 "x 4" (25.4 mm x 101 .6 mm) in dimensions and the joined lap shears overlapped at a 0.5" (12.7 mm) mark and were clamped with Hargrave No.1 clamps. The bonded lap shears were tested using an InstronTM 5567A Materials testing System. The cross-head speed was 6 mm/min.
• Heat ageing was done by packing the parts into two-part cartridges and heating at 35°C in an oven. The effect of the heat ageing was compared by comparison of retention of lap shear tensile strength over time (using test method described above), or noting when the samples could not be dispensed from the cartridges due to gelation or hardening of the compositions.
• Triethylborane mono-2- 12 triethylenediamine complex (Methacryloyloxy)ethyl
• Part A wt.% Part B
• Example 2 shows that removal of the triethylenegylcol divinyl ether reduces the stability of Part A.
• Example 3 shows that similar to example 1 the divinyl ether cyclohexanedimethanol divinyl ether imparts improved stability and better performance in comparison to example 2.
• Triethylborane 2.5 mono-2- 12 triethylenediamine complex (Methacryloyloxy)ethyl
• Example 4 shows that although n-butylvinyl ether imparts better stability and performance than example 2, it does not do so as much so as divinyl ethers in examples 1 and 3.
• Part A wt.% Part B
• Triethylborane 2.5 mono-2- 12 triethylenediamine complex (Methacryloyloxy)ethyl
• Example 5 also shows that the vinyl ether n-hydroxylbutylvinyl ether does not impart stability and performance as well as the divinyl ethers in examples 1 and 3.
• Part A1 (1 Part) wt.% Part B (10 Parts) wt.%
• AerosilTM R 972 5.26 TMPTMA 5
• Part A1 (1 Part) wt.% Part B (10 Parts) wt.%
• Part A1 (1 Part) wt.% Part B (10 Parts) wt.%
• Examples 6 and 7 containing divinyl ethers and borane:amine in the same part show improved stability in comparison to methacrylate ester monomer THFMA and borane:amine in the same part.

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• Polymerization Catalysts (AREA)
• Graft Or Block Polymers (AREA)

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• 2013
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