Crosslinking agent and curable composition containing same

Abstract

Novel crosslinkers and curable compositions containing such crosslinkers are provided. Bonded constructs containing the disclosed curable compositions exhibit high adhesion, elongation, and impact resistance, even when the bonded substrates are not subjected to surface treatment prior to bonding. Elastomeric products containing the curable compositions, methods for their manufacture, and uses are provided.

Description

[Technical Field]

[0001] Crosslinking agents, as well as curable compositions, cured compositions, and articles containing same, are described. [Background technology]

[0002] Structural adhesives are known to be useful for bonding one substrate to another, for example, metal to metal, metal to plastic, plastic to plastic, and glass to glass. Because structural adhesives distribute load stresses over a larger area rather than concentrating them at a few points, structural adhesives are an attractive alternative to mechanical joining methods such as riveting or spot welding. Structural adhesives can also dampen vibrations and reduce noise, resulting in cleaner and quieter products. In addition, structural adhesives can be used to bond a variety of materials, sometimes without extensive surface pretreatment. Summary of the Invention

[0003] In one aspect, formula LR 1 q [In the formula, each R 1 are independently expressed as [ka] (In the formula, Each R 2 are independently hydrogen or methyl; n is an integer between 1 and 5, inclusive; X is O, S, or NH; Y is a single bond or a group of formula [ka] (In the formula, N' is R 1 is the nitrogen bonded to the carbonyl carbon of T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof; q is an integer equal to or greater than 2, L is formula [ka] (In the formula, R 3 is hydrogen or a Z-terminal alkyl or heteroalkylene chain, wherein each Z-terminal chain may independently comprise a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and each Z is independently O, S, or NH. and a) a monomer unit represented by formula [ka] (wherein n is an integer from 1 to 5 (inclusive), and each R 4 are independently hydrogen or alkyl, and each Z is independently O, S, or NH. b) a monomer unit represented by is a q-valent organic polymer containing A compound represented by A cross-linking agent comprising:

[0004] In another aspect, monofunctional monomers, a curing initiator system, and formula LR 1 q [In the formula, each R 1 are independently expressed as [ka] (In the formula, Each R 2 are independently hydrogen or methyl; n is an integer between 1 and 5, inclusive; X is O, S, or NH; Y is a single bond or a group of formula [ka] (In the formula, N' is R 1 is the nitrogen bonded to the carbonyl carbon of T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof. is a divalent group represented by and is selected from functional groups represented by q is an integer equal to or greater than 2, L has a number average molecular weight of 4000 g / mole to 54000 g / mole relative to polystyrene standards and has the formula [ka] (In the formula, R 3 is hydrogen or a Z-terminal alkyl or heteroalkylene chain, wherein each Z-terminal chain independently may include a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and each Z is independently O, S, or NH; [ka] (wherein n is an integer from 1 to 5 (inclusive), and each R 4 is independently hydrogen or alkyl, and each Z is independently O, S, or NH; [ka] (wherein j is an integer of 30 or less, k is an integer of 30 or less, and each R 4 are independently hydrogen or alkyl, and each R 5 independently, C 10 ~C 15 Alkyl group or C 10 ~C15 alkenyl groups, where j and k cannot both be zero, and the moieties having the subscripts j and k are randomly distributed along the carbon chain; [ka] (wherein m is an integer from 10 to 330 (inclusive), and n is an integer from 1 to 5 (inclusive)) and a monomer unit represented by Monomer units selected from the group consisting of mixtures thereof is a q-valent organic polymer containing A compound represented by A curable composition comprising: The organic polymer L having a valence of q contains, if present, monomer units e), less than 26,000 g / mol, relative to the polystyrene standard, of monomer units e), A curable composition is provided.

[0005] In another aspect, there is provided a method of bonding a first substrate to a second substrate, the method comprising: mixing the curable composition of the present disclosure with an accelerator to form an adhesive composition; applying an adhesive composition to at least a portion of one surface of a first substrate; at least partially coating the adhesive composition with at least a portion of one surface of a second substrate; and curing the adhesive composition; A method is provided, comprising:

[0006] In another aspect, there is provided an elastomeric article prepared from at least one of the crosslinkers or curable compositions disclosed herein.

[0007] In another aspect, a bonded article is provided that includes an elastomeric article bonded to a substrate.

[0008] In another aspect, a method of delaminating a first substrate that is attached to a second substrate by elastomeric beads is provided, the method comprising pulling the beads away from at least one of the first substrate or the second substrate, such that the beads stretch-debond from at least one of the first substrate or the second substrate.

[0009] The term "alkyl" refers to a monovalent group that is a radical of an alkane, which is a saturated hydrocarbon. Alkyl can be linear, branched, cyclic, or a combination thereof and typically has 1 to 20 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and ethylhexyl.

[0010] The term "alkylene" refers to a divalent group that is a radical of an alkane. Alkylene can be linear, branched, cyclic, or a combination thereof. Alkylene typically has 1 to 20 carbon atoms. The centers of the alkylene groups can be on the same carbon atom (i.e., alkylidene) or on different carbon atoms.

[0011] The term "alkoxy" refers to a monovalent group of formula -OR where R is alkyl.

[0012] The term "arylene" refers to a polyvalent aromatic group, for example, phenylene, naphthalene, and the like.

[0013] The term "heteroalkylene" refers to thio, oxy, or NR b [In the formula, R bis hydrogen or alkyl. Heteroalkylene may be linear, branched, cyclic, or a combination thereof. Exemplary heteroalkylenes include alkylene oxide or poly(alkylene oxide). That is, the heteroalkylene contains at least one group of the formula -(RO)-, where R is alkylene.

[0014] The terms "(meth)acrylate" or "(meth)acrylic acid" are used herein to refer to the corresponding acrylate and methacrylate. Thus, by way of example, the term "(meth)acrylic acid" includes both methacrylic acid and acrylic acid, and the term "(meth)acrylate" includes both acrylate and methacrylate. (Meth)acrylate or (meth)acrylic acid may consist exclusively of methacrylate or methacrylic acid, respectively, or exclusively of acrylate or acrylic acid, respectively, but may also refer to a mixture of acrylate and methacrylate (or acrylic acid and methacrylic acid), respectively.

[0015] The phrase "comprising at least one of" following a list refers to the inclusion of any one of the items in the list, as well as any combination of two or more items in the list. The phrase "at least one of" following a list refers to any one of the items in the list, or any combination of two or more items in the list.

[0016] As used herein, the term "and / or" is used to indicate that either or both of stated things may occur; for example, A and / or B includes (A and B) and (A or B).

[0017] As used herein, the term "room temperature" refers to a temperature within the range of 20°C to 25°C.

[0018] As used herein, the term "substantially free" means that there is less than 1 wt. %, less than 0.5 wt. %, or less than 0.1 wt. % of a given component in the composition, based on the total weight of the composition.

[0019] The features and advantages of the present disclosure will be further understood by consideration of the detailed description and appended claims.

[0020] It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art which fall within the scope of the principles of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0021] While known structural adhesives may have good high-temperature performance and durability, the hard bonds that these structural adhesives produce after curing can result in poor impact resistance of the bonded parts and subsequent bond failure. In addition, adhesives with hard bonds experience high stresses that are unevenly distributed throughout the bond, with stresses at the edges of the bond typically being greater than the stress in the center of the bond. High stresses on hard structural adhesives can cause undesirable distortion of the bonded material, i.e., bondline sink marks, which can be visually observed, especially when bonding large parts such as automotive panels.

[0022] One approach used in industry to enhance the flexibility and toughness of structural adhesives is to incorporate elastomeric materials that can be dissolved or dispersed in the adhesive composition. Examples of such elastomeric materials include methyl methacrylate-butadiene-styrene copolymer ("MBS"), acrylonitrile-styrene-butadiene copolymer, linear polyurethane, acrylonitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, butadiene rubber, and natural rubber. However, these elastomeric material additives can result in high viscosity liquid adhesive compositions, which can create handling challenges during use. Additionally, in the case of butadiene or other conjugated diene rubbers, the elastomeric material additives can reduce the oxidation resistance of the structural adhesive, potentially leading to bond failure.

[0023] The present disclosure provides curable compositions that, due to the inclusion of novel crosslinkers described below, are substantially free of liquid rubber materials and further result in bonded constructs that exhibit high adhesion (i.e., greater than 1000 psi in a typical overlap shear test), elongation (i.e., values ​​greater than 50%, 100%, or 400%), and impact resistance (i.e., greater than 2 J), even when the bonded substrates (e.g., glass, metal, polymer) are not subjected to surface treatment (e.g., corona, flame, polishing) prior to bonding. The curable compositions in embodiments of the present disclosure may further have the advantages of providing sealants that are resistant to hydrolysis upon aging with heat and / or humidity, resulting in bonded constructs that exhibit little or no bondline sink, and providing adhesive compositions that exhibit stretch-peel, potentially allowing for rework of parts bonded with these adhesives. In some cases, adhesives prepared from the crosslinkers or compositions of the present disclosure allow parts to be separated from each other using heat and non-wire strings.

[0024] Crosslinking agent The crosslinking agent of the present disclosure has the formula LR 1 q [In the formula, each R 1 are independently expressed as [ka] (In the formula, Each R 2 are independently hydrogen or methyl; n is an integer between 1 and 5, inclusive; X is O, S, or NH; Y is a single bond or a group of formula [ka] (In the formula, N' is R 1 is the nitrogen bonded to the carbonyl carbon of T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof. is a divalent group represented by and is selected from functional groups represented by q is an integer equal to or greater than 2, L is the formula [ka] (In the formula, R 3 is hydrogen or a Z-terminal alkyl or heteroalkylene chain, wherein each Z-terminal chain independently may include a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and each Z is independently O, S, or NH; [ka] (wherein n is an integer from 1 to 5 (inclusive), and each R 4 is independently hydrogen or alkyl, and each Z is independently O, S, or NH; [ka] (wherein n is an integer from 1 to 5 (inclusive), and each R 4is independently hydrogen or alkyl, and each Z is independently O, S, or NH; [ka] (wherein j is an integer of 30 or less, k is an integer of 30 or less, and each R 4 are independently hydrogen or alkyl, and each R 5 independently, C 10 ~C 15 Alkyl group or C 10 ~C 15 alkenyl groups, where j and k cannot both be zero, and the moieties having the subscripts j and k are randomly distributed along the carbon chain; [ka] (wherein m is an integer from 10 to 330 (inclusive), and n is an integer from 1 to 5 (inclusive)) and a monomer unit represented by Monomer units selected from the group consisting of mixtures thereof is a q-valent organic polymer containing A compound represented by The q-valent organic polymer L has monomer units e), if present, of a number average molecular weight, relative to polystyrene standard, of less than 26000 grams per mole.

[0025] In some embodiments, L is of the formula [ka] [In the formula, each R 6are independently hydrogen, a monomeric unit selected from the group consisting of monomeric units a) through e), and a Z-terminal alkyl chain, wherein the Z-terminal alkyl chain may include a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and Z is O, S, or NH; and combinations thereof, where it is understood that monomeric units f), g), and h), when present, are not located at the termini of L.

[0026] In some embodiments, L is of the formula [ka] where T is a divalent radical selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof. In such embodiments, L may be a block copolymer having the general structure ABABA, where each A represents a homopolymer including monomer units of formula b) [where n=4 and Z is O] having a number average molecular weight of 2500 g / mole to 3500 g / mole (e.g., 2900 g / mole), and each B represents a monomer unit represented by formula i), where it is understood that monomer unit i), if present, is not located at the terminal end of L. In some embodiments, L may have a number average molecular weight of 4000 g / mole to 40,000 g / mole, or 8,000 g / mole to 30,000 g / mole.

[0027] With respect to the q-valent organic polymer L, it is understood that L can be a homopolymer or a copolymer (e.g., block copolymer, random copolymer). For example, a homopolymer L will contain only one type of monomer unit, i.e., a), b), c), d), or e), in the polymer chain. A block copolymer can, for example, contain a sequence of a) monomer units adjacent to a sequence of b) monomer units to form the polymer chain. A random copolymer can, for example, contain a number of a first number of b) monomer units randomly interspersed with a number of a second number of a) monomer units to form the polymer chain.

[0028] Expression LR 1 q The crosslinker of the present disclosure, represented by the formula (I), can be prepared by methods known to those skilled in the art and described, for example, in Cooper, S.L. and Guan, J. (Eds) "Advances in Polyurethane Biomaterials", Chapter 4, (Elsevier Ltd., 2016) and Lin et al., "UV-curable low-surface-energy fluorinated poly(urethane-acrylates)s for biomedical applications", European Polymer Journal, Vol. 44, pp. 2927-2937 (2008). For example, a crosslinker comprising monomer units represented by formulas a) and b) can be prepared by reacting a polyether polyprimary polyamine, either available from 3M Company (St. Paul, MN) under the trade name DYNAMAR HC-1101, or prepared as described in U.S. Pat. No. 3,436,359 (Hubin et al.), with 2-isocyanatoethyl methacrylate ("IEM").

[0029] In some embodiments, the q-valent organic polymer L comprises 10% to 20% by weight of monomers of monomer unit a) and at least 70% by weight of monomers of monomer unit b). In some embodiments, the q-valent organic polymer L comprises less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, or less than 0.5% by weight of monomers of monomer unit a), and R 3 is not hydrogen. In some embodiments, the q-valent organic polymer L has a number average molecular weight, relative to polystyrene standards, of 4000 grams / mole to 54000 grams / mole.

[0030] curable composition The curable compositions of the present disclosure generally have the formula LR 1 q The curing agent comprises a crosslinker compound represented by the formula:

[0031] The curable compositions of the present disclosure generally comprise from 2% to 60% by weight or from 5% to 50% by weight of a compound of formula LR 1 q (above) includes compounds represented by:

[0032] Monofunctional Monomers The curable composition further comprises a monofunctional monomer. Examples of monofunctional (meth)acrylate monomers useful in embodiments of the present disclosure include 2-phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, acid-functional monomers such as (meth)acrylic acid, alkoxylated lauryl (meth)acrylate, alkoxylated phenol (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, caprolactone (meth)acrylate, cyclic trimethylolpropane formyl (meth)acrylate, ethylene glycol methyl ether methacrylate, ethoxylated nonylphenol (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), tetrahydrofurfuryl (meth)acrylate, acrylate, tridecyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, allyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-Dodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- and 3-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2- or 3-ethoxypropyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, glycidyl (meth)acrylate, phosphonate-functional (meth)acrylate monomers (e.g., SIPOMER PAM resins from Solvay Specialty Polymers USA, LLC, or Miwon North America (Exton,Resins available under the trade names MIRAMER SC1400 and MIRAMER SC1400A from Solvay Specialty Polymers USA, LLC), N-(2-(2-oxo-1-imidazolidinyl)ethyl)-methacrylamide (methacrylamidoethyl ethylene urea ("MAEEU") available under the trade name SIPOMER WAM II from Solvay Specialty Polymers USA, LLC), and combinations thereof.

[0033] Specific examples of monoacrylate monomers useful in embodiments of the present disclosure include isobornyl acrylate (commercially available from Sartomer under the trade name SR506 or from Evonik Performance Materials GmbH under the trade name VISIOMER IBOA), isobornyl methacrylate (commercially available from Sartomer under the trade name SR423A or from Evonik Performance Materials GmbH under the trade name VISIOMER IBOMA), 2-phenoxyethyl methacrylate (commercially available from Sartomer under the trade name SR340), cyclohexyl methacrylate (commercially available from Evonik Performance Materials GmbH under the trade name VISIOMER c-HMA), benzyl methacrylate (commercially available from Miwon North America (Exton, PA) under the trade name MIRAMER M1183), phenyl methacrylate (commercially available from Miwon North America (Exton, PA) under the trade name MIRAMER M1183), and phenyl methacrylate (commercially available from Miwon North America (Exton, PA) under the trade name MIRAMER M1183).PA) under the trade name MIRAMER M1041), allyl methacrylate (available commercially from Evonik Performance Materials GmbH under the trade name VISIOMER AMA), 2-hydroxyethyl methacrylate (available commercially from Evonik Performance Materials GmbH under the trade name VISIOMER HEMA 97 and HEMA 98), hydroxypropyl methacrylate (available commercially from Evonik Performance Materials GmbH under the trade name VISIOMER HPMA 97 and HPMA 98), ultra-pure 2-hydroxyethyl methacrylate (available commercially from Evonik Performance Materials GmbH under the trade name VISIOMER UHP HEMA), methyl methacrylate (available commercially from Evonik Performance Materials GmbH under the trade name VISIOMER MMA), methacrylic acid (available commercially from Evonik Performance Materials GmbH under the trade name VISIOMER GMAA), n-butyl methacrylate (available commercially from Evonik Performance Materials GmbH under the trade name VISIOMER n-BMA), isobutyl methacrylate (available commercially from Evonik Performance Materials GmbH under the trade name VISIOMER i-BMA), glycerol formal methacrylate (commercially available from Evonik Performance Materials GmbH under the trade name VISIOMER GLYFOMA), 2-(2-butoxyethoxy)ethyl methacrylate (commercially available from Evonik Performance Materials GmbH under the trade name VISIOMER BDGMA), lauryl methacrylate (commercially available from BASF, Florham Park, NJ under the trade name LMA 1214 F), polypropylene glycol monomethacrylate (Miwon North America, Exton,(Commercially available under the trade name MIRAMER M1051 from Shin-Nakamura Chemical Co., Ltd., Arimoto, Japan), β-methacryloyloxyethyl hydrogen succinate (Commercially available under the trade name NK Ester SA from Shin-Nakamura Chemical Co., Ltd., Arimoto, Japan), 2-isocyanatoethyl methacrylate (Commercially available under the trade name Karenz MOI from Showa Denko K.K., Tokyo, Japan), 2-(methacryloyloxy)ethyl phthalate mono (HEMA phthalate) commercially available from ESSTECH, Inc., Essington, PA as product number X-821-2000 2-(methacryloyloxy)ethyl maleate (HEMA maleate) available from ESSTECH, Inc. (Essington, PA) under product number X-846-0000; methoxydiethylene glycol methacrylate (available from Shin-Nakamura Chemical Co., Ltd. (Arimoto, Japan) under the trade name M-20G; methoxytriethylene glycol methacrylate (available from Shin-Nakamura Chemical Co., Ltd. (Arimoto, Japan) under the trade name M-30G; methoxytetraethylene glycol methacrylate (available from Shin-Nakamura Chemical Co., Ltd. (Arimoto, Japan) under the trade name M-40G); Glycol methacrylate (commercially available from Shin-Nakamura Chemical Co., Ltd. (Arimoto, Japan) under the trade name M-40G), methoxytripropylene glycol methacrylate (commercially available from Shin-Nakamura Chemical Co., Ltd. (Arimoto, Japan) under the trade name M-30PG), butoxydiethylene glycol methacrylate (commercially available from Shin-Nakamura Chemical Co., Ltd. (Arimoto, Japan) under the trade name B-20G), and phenoxyethylene glycol methacrylate (commercially available from Shin-Nakamura Chemical Co., Ltd. (Arimoto, Japan) under the trade name PHE-1G). commercially available under the trade name), phenoxydiethylene glycol methacrylate (commercially available under the trade name PHE-2G from Shin-Nakamura Chemical Co., Ltd. (Arimoto, Japan)), dicyclopentenyloxyethyl methacrylate (commercially available under the trade name Fancryl FA-512M from Hitachi Chemical Co., Ltd. (Tokyo, Japan)), dicyclopentanyl methacrylate (commercially available under the trade name Fancryl FA-513M from Hitachi Chemical Co., Ltd. (Tokyo, Japan), and isobornylcyclohexyl methacrylate (Designer Molecules, Inc. (San Diego,Examples of suitable acrylic acid esters include 4-methacryloxyethyl trimellitic anhydride (available from Designer Molecules, Inc., San Diego, CA, as product MM-304), 4-methacryloxyethyl trimellitic anhydride (available from Designer Molecules, Inc., San Diego, CA, as product A-304), 2-methacryloxyethyl phenyl urethane (available from Polysciences, Inc., Warrington, PA), trifluoroethyl methacrylate (available from Hampford Research Inc., Stratford, CT), methacrylamide (available from Evonik Performance Materials GmbH under the trade name VISIOMER MAAmide), 2-dimethylaminoethyl methacrylate (available from Evonik Performance Materials GmbH under the trade name VISIOMER MADAME), 3-dimethylaminopropyl methacrylamide (available from Evonik Performance Materials GmbH under the trade name VISIOMER DMAPMA), and combinations thereof.

[0034] In some embodiments, the monofunctional (meth)acrylate monomer may act as a reactive diluent for the oligomer.

[0035] In some embodiments, the monofunctional monomer is selected from the group consisting of methyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid, 2-(2-butoxyethoxy)ethyl methacrylate, glycerol formal methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and combinations thereof.

[0036] In embodiments of the present disclosure, the curable composition generally comprises 49% to 97% by weight of monofunctional monomer.

[0037] Curing initiator system The curable composition further comprises a curing initiator system. In some embodiments, the curing initiator system is a redox initiator system, since one-electron transfer redox reactions can be an effective method for generating free radicals under mild conditions. Redox initiator systems are described, for example, in Prog. Polym. Sci. 24 (1999) 1149-1204.

[0038] In some embodiments, the redox initiator system is a blend of peroxide and amine, where polymerization is initiated by decomposition of the organic peroxide activated by a redox reaction with an amine reducing agent. Typically, the peroxide is benzoyl peroxide and the amine is a tertiary amine. Aromatic tertiary amines are the most effective compounds for generating primary radicals, and N,N-dimethyl-4-toluidine ("DMT") is the most common amine reducing agent.

[0039] In some embodiments, the redox cure initiator system comprises a barbituric acid derivative and a metal salt. In some embodiments, the barbituric acid / metal salt cure initiator system may further comprise an organic peroxide, an ammonium chloride salt (e.g., benzyltributylammonium chloride), or a mixture thereof.

[0040] Examples of barbituric acid-based curing initiator systems include (i) barbituric acid derivatives and / or malonyl sulfamides, and (ii) redox initiator systems having organic peroxides selected from the group consisting of monofunctional or polyfunctional percarboxylic acid esters.As barbituric acid derivatives, for example, 1,3,5-trimethylbarbituric acid, 1,3,5-triethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,5-dimethylbarbituric acid, 1-methyl-5-ethylbarbituric acid, 1-methyl-5-propylbarbituric acid, 5-ethylbarbituric acid, 5-propylbarbituric acid, 5-butylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and thiobarbituric acid can be used, as mentioned in German Patent Application DE-A-4219700.

[0041] Barbituric acids and barbituric acid derivatives described in U.S. Patent Nos. 3,347,954 (Bredereck et al.) and 9,957,408 (Thompson) and malonyl sulfamides disclosed in European Patent Specification EP-B-0059451 may be useful in embodiments of the present disclosure. Examples of malonyl sulfamides include 2,6-dimethyl-4-isobutylmalonyl sulfamide, 2,6-diisobutyl-4-propylmalonyl sulfamide, 2,6-dibutyl-4-propylmalonyl sulfamide, 2,6-dimethyl-4-ethylmalonyl sulfamide, or 2,6-dioctyl-4-isobutylmalonyl sulfamide.

[0042] Barbituric acid-based redox initiator systems typically contain monofunctional or polyfunctional carboxylic acid peroxyesters as organic peroxides. Carbonic acid peroxyesters are also included in the polyfunctional carboxylic acid peroxyesters in the sense of the present disclosure. Suitable examples include diisopropyl carbonate peroxydiester, tert-butyl neodecanoate peroxyester, tert-amyl neodecanoate peroxyester, tert-butyl maleate monoperoxyester, tert-butyl benzoate peroxyester, tert-butyl 2-ethylhexanoate peroxyester, tert-amyl 2-ethylhexanoate peroxyester, monoisopropyl carbonate monotert-butyl peroxyester, dicyclohexyl carbonate peroxyester, and dimyristyl carbonate peroxyester. , dicetyl carbonate peroxyester, di(2-ethylhexyl) carbonate peroxyester, tert-butyl carbonate peroxy(2-ethylhexyl) ester, or tert-butyl 3,5,5-trimethylhexanoic acid peroxyester, tert-amyl benzoic acid peroxyester, tert-butyl acetate peroxyester, di(4-tert-butylcyclohexyl) carbonate peroxyester, cumene neodecanoic acid peroxyester, tert-amyl pivalic acid peroxyester, and tert-butyl pivalic acid peroxyester.

[0043] In particular, tertiary-butyl-peroxy(2-ethylhexyl)carbonate (commercially available under the trade name LUPEROX TBEC from Arkema, Inc., King of Prussia, PA) or tertiary-butyl-3,5,5-trimethyl-hexanoic acid peroxyester (commercially available under the trade name LUPEROX 270 from Arkema, Inc., King of Prussia, PA) can be used as the organic peroxide according to embodiments of the present disclosure.

[0044] Metal salts that may be used with the barbituric acid derivatives include transition metal complexes, particularly salts of cobalt, manganese, copper, and iron. When the metal salt is a copper compound, the salt has the general formula CuX n where X is an organic and / or inorganic anion and n=1 or 2. Examples of suitable copper salts include copper chloride, copper acetate, copper acetylacetonate, copper naphthenate, copper salicylate, or complexes of copper with thiourea or ethylenediaminetetraacetic acid, and mixtures thereof. In some embodiments, the copper compound is copper naphthenate.

[0045] Another redox initiator system suitable for use in embodiments of the present disclosure includes an inorganic peroxide, an amine-based reducing agent, and an accelerator, where the amine can be an aromatic and / or aliphatic amine, and the polymerization accelerator is at least one selected from the group consisting of sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate, sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfate, and potassium bisulfate. An example of an inorganic peroxide useful in this system is peroxodisulfate, as described in U.S. Pat. No. 8,545,225 (Takei, et al.).

[0046] In some embodiments, the curable composition comprises a curing initiator system comprising a metal salt (e.g., copper naphthenate) and an ammonium salt (e.g., benzyltributylammonium chloride). In some embodiments, the curable composition comprises a curing initiator system comprising a barbituric acid derivative and a metal salt, and optionally at least one of an organic peroxide and an ammonium chloride salt.

[0047] The curable composition may also include at least one photoinitiator, which means that the initiator is activated by light, generally ultraviolet (UV) light, although other light sources can be used by selecting an appropriate initiator, such as a visible light initiator or an infrared light initiator. Typically, a UV photoinitiator is used.

[0048] Useful photoinitiators include those known to be useful for free-radically photocuring polyfunctional (meth)acrylates. Exemplary photoinitiators include benzoin and its derivatives, such as α-methylbenzoin; α-phenylbenzoin; α-allylbenzoin; α-benzylbenzoin; benzoin ethers, such as benzil dimethyl ketal (e.g., "OMNIRAD BDK" from IGM Resins USA Inc., St. Charles, IL), benzoin methyl ether, benzoin ethyl ether, and benzoin n-butyl ether; acetophenone and its derivatives, such as 2-hydroxy-2-methyl-1-phenyl-1-propanone (e.g., available under the trade name OMNIRAD 1173 from IGM Resins USA Inc., St. Charles, IL), and 1-hydroxycyclohexyl phenyl ketone (e.g., available under the trade name OMNIRAD 184 from IGM Resins USA Inc., St. Charles, IL); 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone (e.g., available under the trade name OMNIRAD 184 from IGM Resins USA Inc., St. Charles, IL), and 1-hydroxycyclohexyl phenyl ketone (e.g., available under the trade name OMNIRAD 184 from IGM Resins USA Inc., St. Charles, IL). Inc. (St. Charles, IL) under the trade name OMNIRAD 907); 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (e.g., available from IGM Resins USA Inc. (St. Charles, IL) under the trade name OMNIRAD 369), and phosphine oxide derivatives such as ethyl-2,4,6-trimethylbenzoylphenylphosphinate (e.g., available from IGM Resins USA Inc. (St. Charles, IL) under the trade name TPO-L), and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (e.g., available from IGM Resins USA Inc. (St. Charles, IL) under the trade name OMNIRAD 819).

[0049] Other useful photoinitiators include, for example, pivaloin ethyl ether, anisoin ethyl ether, anthraquinones (e.g., anthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, 1,4-dimethylanthraquinone, 1-methoxyanthraquinone, or benzanthraquinone), halomethyltriazines, benzophenone and its derivatives, iodonium and sulfonium salts, titanium complexes such as bis(etha5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (available, for example, under the tradename CGI 784DC from BASF, Florham Park, NJ); halomethyl-nitrobenzenes (e.g., 4-bromomethylnitrobenzene), and photoinitiator combinations in which one component is a mono- or bis-acylphosphine oxide (e.g., IRGACURE 1700, IRGACURE 1700, and the like, available from BASF, Florham Park, NJ). and available from IGM Resins USA Inc. (St. Charles, IL) under the tradename OMNIRAD 4265.

[0050] Generally, the photoinitiator is used in an amount of 0.01 to 10 parts by weight, more typically 0.1 to 2.0 parts by weight, based on 100 parts by weight of all reactive components.

[0051] The components of the cure initiator system are present in the curable composition in amounts sufficient to cure the curable composition at an appropriate free radical reaction rate upon initiation of polymerization, an amount that can be readily determined by one skilled in the art. In embodiments of the present disclosure, the curable composition generally comprises from 0.1 wt % to 10 wt %, or from 0.5 wt % to 5 wt %, of the cure initiator system.

[0052] additives The curable composition may optionally contain one or more conventional additives, which may include, for example, tackifiers, plasticizers, dyes, pigments, antioxidants, UV stabilizers, corrosion inhibitors, dispersants, wetting agents, adhesion promoters, and fillers.

[0053] Fillers useful in embodiments of the present disclosure include, for example, fillers selected from the group consisting of microfibrillated polyethylene, fumed silica, talc, wollastonite, aluminosilicate clays (e.g., halloysite), phlogopite mica, calcium carbonate, kaolin clay, metal oxides (e.g., barium oxide, calcium oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide), nanoparticle fillers (e.g., nanosilica, nanozirconia), and combinations thereof.

[0054] Elastomer products Expression LR 1 q Crosslinkers of the present disclosure, represented by: and curable compositions comprising such crosslinkers, can be used to form elastomeric products such as adhesives and sealants.

[0055] Elastomeric products can be prepared by methods known to those skilled in the art, such as by curing the curable compositions disclosed herein. For example, an adhesive or sealant comprising a curable composition of the present disclosure can be prepared by combining the curable composition of the present disclosure with an accelerator, such as the accelerator from 3M SCOTCH-WELD DP8410NS acrylic adhesive (3M Company, St. Paul, Minn.), and curing the resulting combination. In some embodiments, the adhesive or sealant can include 10 parts curable composition and 1 part accelerator.

[0056] In some embodiments, the elastomeric articles have a minimum ultimate elongation of at least 50%, at least 100%, at least 200%, at least 400%, at least 600%, or at least 800%, and / or a minimum lap shear strength of at least 1000 psi, at least 1100 psi, at least 1200 psi, at least 1300 psi, or at least 1400 psi. The tensile elongation and lap shear strength of the elastomers are measured using the test methods in the Examples below. In some embodiments, the elastomeric articles may exhibit stretch peeling. In some embodiments, the elastomeric articles may be resistant to hydrolysis upon aging with heat and / or humidity.

[0057] The tan δ peak in dynamic mechanical analysis ("DMA") reflects a material's ability to store or dissipate energy. A broader tan δ peak suggests that the material can dissipate energy and survive impacts over a wider range of frequencies and / or temperatures.

[0058] In some embodiments, the elastomeric article may exhibit an impact resistance of greater than 2 J, greater than 3 J, greater than 4 J, or greater than 5 J when dropped from an angle of 150.0° using a 21.6 J hammer using the testing parameters of ISO 179-1.

[0059] The elastomeric products of the present disclosure can be used, for example, to bond a first substrate to a second substrate to provide a bonded article. Many types of substrates, such as metals (e.g., aluminum), plastics (e.g., polyamides), and glass, can be bonded using the elastomeric products of the present disclosure. In some embodiments, a first substrate can be bonded to a second substrate by mixing a curable composition of the present disclosure with an accelerator to form an adhesive composition, applying the adhesive composition to at least a portion of one surface of the first substrate, at least partially coating the adhesive composition with at least a portion of one surface of the second substrate, and curing the adhesive composition. In some embodiments, a portion of one surface of the first substrate has not been subjected to a surface treatment (e.g., corona, flame, polishing) prior to applying the adhesive composition thereto. In some embodiments, a portion of one surface of the second substrate has not been subjected to a surface treatment (e.g., corona, flame, polishing) prior to contact with the adhesive composition. In some embodiments, the first substrate and the second substrate are made of different materials, such as metal and plastic or metal and glass. In some embodiments, the bonded article can be, for example, an automobile part, an electronic device, or a component of an electronic device.

[0060] After curing, the curable compositions provide bonded constructs on a variety of substrates that exhibit high adhesion, elongation, and impact resistance, even when the bonded substrates are not surface-treated prior to bonding. The curable compositions of the present disclosure may provide adhesives that provide bonded constructs that exhibit little or no bondline sink, which may be particularly useful in automotive and aerospace applications, among others. The curable compositions of the present disclosure may provide adhesives that are particularly suitable for use in portable electronic devices, which require tough adhesives that can withstand impacts associated with drop tests. The curable compositions of the present disclosure may provide adhesive compositions that exhibit stretch-peeling, allowing components to be disassembled using heat and non-wire strings, both of which may enable rework of parts bonded by these adhesives. For example, in bonding glass lens components to metal or plastic frames, the cured adhesive beads may be stretch-peeled and pulled from the bonded substrates, often exhibiting a clean release without leaving any visible adhesive residue. Furthermore, the elastomeric properties of the adhesive can allow the components to be separated using heat and a non-wire string, such as dental floss or fishing line. For example, a non-wire string can be pulled through the bonded area between two substrates while applying heat of up to 65°C, at which point the two substrates can be easily separated. Once the components are separated, the adhesive can be pulled to stretch it, cleanly removing it from either surface; typically, the adhesive is removed in a single strand. The curable compositions of the present disclosure can provide sealants that are resistant to hydrolysis upon aging due to heat or humidity, which can be particularly useful in applications where the sealant is exposed to warm, humid conditions for extended periods of time.

[0061] Selected Embodiments of the Present Disclosure In the first embodiment, formula LR 1 q [In the formula, each R 1 are independently expressed as [ka] (In the formula, Each R 2 are independently hydrogen or methyl; n is an integer between 1 and 5, inclusive; X is O, S, or NH; Y is a single bond or a group of formula [ka] (In the formula, N' is R 1 is the nitrogen bonded to the carbonyl carbon of T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof; q is an integer equal to or greater than 2, L is formula [ka] (In the formula, R 3 is hydrogen or a Z-terminal alkyl or heteroalkylene chain, wherein each Z-terminal chain may independently comprise a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and each Z is independently O, S, or NH. and a) a monomer unit represented by formula [ka] (wherein n is an integer from 1 to 5 (inclusive), and each R 4 are independently hydrogen or alkyl, and each Z is independently O, S, or NH. b) a monomer unit represented by is a q-valent organic polymer containing A compound represented by A cross-linking agent comprising:

[0062] In a second embodiment, there is provided the crosslinker according to the first embodiment, wherein the q-valent organic polymer L has a number average molecular weight of 4,000 g / mole to 54,000 g / mole relative to a polystyrene standard.

[0063] In a third embodiment, there is provided the crosslinking agent according to the first or second embodiment, wherein the q-valent organic polymer L contains 10% by weight to 20% by weight of the monomer unit a).

[0064] In a fourth embodiment, there is provided a crosslinker according to any one of the first to third embodiments, wherein the q-valent organic polymer L comprises at least 70% by weight of monomer units b).

[0065] In a fifth embodiment, the q-valent organic polymer L comprises less than 7 wt.%, less than 6 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, less than 1 wt.%, or less than 0.5 wt.% of monomer units a) and R 3 The cross-linking agent according to any one of the first to fourth embodiments is provided, wherein is not hydrogen.

[0066] In the sixth embodiment, monofunctional monomers, a curing initiator system, and formula LR 1 q [In the formula, each R 1 are independently expressed as [ka] (In the formula, Each R 2 are independently hydrogen or methyl; n is an integer between 1 and 5, inclusive; X is O, S, or NH; Y is a single bond or a group of formula [ka] (In the formula, N' is R 1 is the nitrogen bonded to the carbonyl carbon of T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof. is a divalent group represented by and is selected from functional groups represented by q is an integer equal to or greater than 2, L has a number average molecular weight of 4000 g / mole to 54000 g / mole relative to polystyrene standards and has the formula [ka] (In the formula, R 3 is hydrogen or a Z-terminal alkyl or heteroalkylene chain, wherein each Z-terminal chain independently may include a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and each Z is independently O, S, or NH; [ka] (wherein n is an integer from 1 to 5 (inclusive), and each R 4 is independently hydrogen or alkyl, and each Z is independently O, S, or NH; [ka] (wherein j is an integer of 30 or less, k is an integer of 30 or less, and each R 4 are independently hydrogen or alkyl, and each R 5 independently, C 10 ~C 15 Alkyl group or C 10 ~C 15 alkenyl groups, where j and k cannot both be zero, and the moieties having the subscripts j and k are randomly distributed along the carbon chain; [ka] (wherein m is an integer from 10 to 330 (inclusive), and n is an integer from 1 to 5 (inclusive)) and a monomer unit represented by Monomer units selected from the group consisting of mixtures thereof is a q-valent organic polymer containing A compound represented by A curable composition comprising: The q-valent organic polymer L has, if present, monomer units e), a number average molecular weight, relative to polystyrene standards, of less than 26,000 g / mol; A curable composition is provided.

[0067] In a seventh embodiment, there is provided the curable composition of the sixth embodiment, wherein the monofunctional monomer is selected from the group consisting of methyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid, 2-(2-butoxyethoxy)ethyl methacrylate, glycerol formal methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and combinations thereof.

[0068] In an eighth embodiment, there is provided a curable composition according to the sixth or seventh embodiment, wherein the curing initiator system comprises a free radical initiator system.

[0069] In a ninth embodiment, there is provided the curable composition according to any one of the sixth to eighth embodiments, wherein the q-valent organic polymer L comprises 10% by weight to 20% by weight of the monomer unit a).

[0070] In a tenth embodiment, the q-valent organic polymer L is of the formula [ka] [wherein n is an integer of 1 to 5 (inclusive), and each R 4are independently hydrogen or alkyl, and each Z is independently O, S, or NH. The curable composition according to any one of the sixth to ninth embodiments is provided, further comprising a monomer unit b represented by:

[0071] In an eleventh embodiment, there is provided a curable composition according to the tenth embodiment, wherein the q-valent organic polymer L comprises at least 70% by weight of monomers of monomer units b).

[0072] In a twelfth embodiment, the q-valent organic polymer L comprises less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, or less than 0.5 wt% of monomer units a) and R 3 The curable composition according to any one of the sixth to eleventh embodiments, wherein is not hydrogen.

[0073] In a thirteenth embodiment, the q-valent organic polymer L is of the formula [ka] [In the formula, each R 6 are independently hydrogen, a monomeric unit selected from the group consisting of monomeric units a) through e), and a Z-terminal alkyl chain, wherein the Z-terminal alkyl chain may include a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and Z is O, S, or NH. The curable composition according to any one of the sixth to twelfth embodiments is provided, further comprising a monomer unit selected from the group consisting of monomer units represented by: and combinations thereof.

[0074] In a fourteenth embodiment, the q-valent organic polymer L is of the formula [ka] wherein T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof. The curable composition according to any one of the sixth to thirteenth embodiments is provided, further comprising a monomer unit represented by:

[0075] In a fifteenth embodiment, the curing agent comprises 49% to 97% by weight of a monofunctional monomer, 0.1% to 10% by weight of a curing initiator system, and 2% to 60% by weight of a compound of formula LR 1 q The curable composition according to any one of the sixth to thirteenth embodiments is provided, comprising a compound represented by:

[0076] In a sixteenth embodiment, there is provided the curable composition according to any one of the sixth to thirteenth embodiments, further comprising a filler.

[0077] In a seventeenth embodiment, there is provided the curable composition of the sixteenth embodiment, wherein the filler is selected from the group consisting of microfibrillated polyethylene, fumed silica, talc, wollastonite, aluminosilicate clays, phlogopite mica, calcium carbonate, kaolin clay, and combinations thereof.

[0078] In an eighteenth embodiment, an elastomeric product is provided prepared from the crosslinker according to any one of the first to fifth embodiments.

[0079] In a nineteenth embodiment, an elastomeric article is provided prepared from the curable composition according to any one of the sixth to seventeenth embodiments.

[0080] In a twentieth embodiment, there is provided an elastomeric article according to the eighteenth or nineteenth embodiment, having a minimum ultimate elongation of at least 50%, at least 100%, or at least 400%.

[0081] In a twenty-first embodiment, there is provided an elastomeric product according to any one of the eighteenth to twentieth embodiments, providing a minimum lap shear strength of at least 1000 psi.

[0082] In a 22nd embodiment, there is provided an elastomeric product according to any one of the 18th to 21st embodiments, wherein the elastomeric product is selected from the group consisting of adhesives and sealants.

[0083] In a 23rd embodiment, there is provided a method of bonding a first substrate to a second substrate, comprising: mixing the curable composition according to any one of the sixth to seventeenth embodiments with an accelerator to form an adhesive composition; applying an adhesive composition to at least a portion of one surface of a first substrate; at least partially coating the adhesive composition with at least a portion of one surface of a second substrate; and curing the adhesive composition; A method is provided, comprising:

[0084] In a 24th embodiment, the method of the 23rd embodiment is provided, wherein 10 parts of the curable composition are mixed with 1 part of the accelerator.

[0085] In a 25th embodiment, there is provided a method according to the 23rd or 24th embodiment, wherein at least one of the first substrate or the second substrate is a polyamide.

[0086] In a 26th embodiment, there is provided a method according to any one of the 23rd to 25th embodiments, wherein the first substrate and the second substrate are different materials.

[0087] In a 27th embodiment, there is provided a method according to any one of the 23rd to 26th embodiments, wherein a portion of one surface of the first substrate has not been subjected to a surface treatment prior to applying the adhesive composition thereto.

[0088] In a twenty-eighth embodiment, a bonded article is provided, comprising the elastomeric product of any one of the eighteenth to twenty-second embodiments bonded to a substrate.

[0089] In a twenty-ninth embodiment, a bonded article is provided, comprising a glass lens bonded to a metal body using the elastomeric article of any one of the eighteenth to twenty-second embodiments.

[0090] In a 30th embodiment, there is provided a method for delaminating a first substrate that is bonded to a second substrate by a bead of an elastomeric product according to any one of the 18th to 22nd embodiments, comprising: A method is provided that includes detaching beads from at least one of a first substrate or a second substrate, where the beads stretch-detach from at least one of the first substrate or the second substrate.

[0091] In a thirty-first embodiment, there is provided a method according to the thirtieth embodiment, wherein the beads are stretched and cleanly released from at least one of the first substrate or the second substrate.

[0092] In a thirty-second embodiment, there is provided a method for delaminating a first substrate bonded to a second substrate along a bondline formed by a bead of cured elastomeric product according to any one of the eighteenth to twenty-second embodiments, comprising: A method is provided that includes pulling the bead away from the bondline, where the bead stretches and is cleanly released from the first and second substrates.

[0093] In a 33rd embodiment, there is provided a method according to any one of the 30th to 32nd embodiments, wherein the beads are removed in one continuous piece from at least one of the first substrate or the second substrate.

[0094] In a 34th embodiment, there is provided a method according to any one of the 30th to 33rd embodiments, wherein the first substrate is a glass lens and the second substrate is a frame, and the method comprises laterally pulling the beads away from the glass lens and the frame, so that the beads stretch-peel away from the glass lens and the frame.

[0095] In a thirty-fifth embodiment, there is provided a method according to any one of the thirty-fourth to thirty-fourth embodiments, further comprising heating at least one of the elastomeric article, the first substrate, or the second substrate prior to drawing the bead of the elastomeric article.

[0096] In a thirty-sixth embodiment, the method of any one of the thirty-fifth to thirty-fifth embodiments is provided, further comprising heating the elastomeric article prior to drawing the bead of the elastomeric article.

[0097] In a thirty-seventh embodiment, the method of any one of the thirty-first to thirty-sixth embodiments is provided, further comprising pulling a non-metallic string through the elastomeric article between the first substrate and the second substrate to separate the first substrate and the second substrate.

[0098] In a thirty-eighth embodiment, the method of the thirty-seventh embodiment is provided, wherein the non-metallic string is dental floss or fishing line.

[0099] In a thirty-ninth embodiment, there is provided a method for removing a glass lens that is bonded to a frame by a bead of an elastomeric product according to any one of the eighteenth to twenty-second embodiments, comprising: A method is provided that includes laterally separating the beads from the glass lens and frame, whereby the beads stretch-release from the glass lens and frame.

[0100] In a fortieth embodiment, A thirty-ninth embodiment provides a method, further comprising heating the glass lens, the frame, and the beads before the drawing step.

[0101] In a forty-first embodiment, there is provided a method according to the thirty-ninth or fortieth embodiment, wherein the beads are stretch-released in one continuous piece from the glass lens and frame.

[0102] In a 42nd embodiment, there is provided a method according to any one of the 39th to 41st embodiments, further comprising pulling a non-metallic string through the elastomeric article between the glass lens and the frame to separate the glass lens and the frame.

[0103] In a 43rd embodiment, the method of the 42nd embodiment is provided, wherein the non-metallic string is dental floss or fishing line.

[0104] The objects and advantages of the present disclosure are further illustrated by the following non-limiting examples, but the specific materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed as unduly limiting the present disclosure. [Example]

[0105] Unless otherwise stated, all parts, percentages, ratios, etc. in the examples and elsewhere in this specification are by weight. [Table 1-1] [Table 1-2]

[0106] Analysis procedure Attenuated Total Reflectance ("ATR") FTIR Spectroscopy ATR-FTIR measurements were recorded using a Thermo Nicolet iS50 FTIR (Thermo Fisher Scientific Co., Waltham, MA, USA) spectrometer equipped with a single-reflection diamond crystal and a deuterated triglycine sulfate detector. A drop of each liquid sample was placed directly on the surface of the diamond ATR crystal, allowing the evanescent wave to be absorbed by the liquid sample. The resulting decaying radiation produced an ATR spectrum similar to a conventional absorption spectrum.

[0107] Transmission FTIR spectroscopy Transmission FTIR measurements were recorded using a Thermo Nicolet iS5 System FTIR (Thermo Fisher Scientific Co., Waltham, MA) spectrometer. Samples are prepared by diluting an aliquot of the reactant in toluene to prepare a solution, spreading the solution on a salt plate, and drying under a stream of nitrogen.

[0108] Gel permeation chromatography Polymers were analyzed by gel permeation chromatography (GPC) using a Reliant GPC (Waters e2695 pump / autosampler) equipped with a Waters 2424 evaporative light scattering detector and PL-Gel-2 columns (each 300 × 7.5 mm; one 3 μm Mixed-E (nominal MW range up to 30,000 Daltons) and one 5 μm Mixed-D (nominal MW range 200 Daltons to 400,000 Daltons)) at 40 °C in tetrahydrofuran stabilized with 250 ppm BHT against polystyrene standards.

[0109] Overlap shear test Each sample formulation was individually loaded into 10 sides of a 10:1 dual syringe cartridge dispenser, and in each case, an accelerator from 3M SCOTCH-WELD DP8410NS acrylic adhesive (3M Company) was used in one side of the dispenser. All bonds were prepared by dispensing the sample formulation and accelerator through a static mixing tip. The resulting adhesive was used to prepare overlap shear test specimens on grit-blasted aluminum substrates. The overlap shear specimens were 2.54 cm x 10.16 cm x 0.16 cm aluminum coupons with 0.076 mm to 0.0127 mm spacer beads and had a 1.27 cm overlap. The bondline was clamped with binder clips during cure, and the clips were removed after 24 hours at 25°C. The overlap shear test was performed with a 5000 lb (22 kN) load cell. Values ​​are the average of three specimens.

[0110] Impact Test Each sample formulation was individually loaded into 10 sides of a 10:1 dual syringe cartridge dispenser, and in each case, an accelerator from SCOTCH-WELD DP8410NS acrylic adhesive (3M Company) was used in one side of the dispenser. All bonds were prepared by dispensing the sample formulation and accelerator through a static mixing tip to form an adhesive composition, which was then used to prepare impact test specimens on grit-blasted aluminum substrates. Impact specimens were 2.54 cm x 10.16 cm x 0.16 cm aluminum coupons with 0.076 mm to 0.0127 mm spacer beads and a 1.27 cm overlap. The bondline was clamped with binder clips during cure, and the clips were removed after 24 hours at 25°C. The specimens were tested in an Instron CP9050 Impact Pendulum, holding the specimen in the clamp and impacting the edge of the bonded area. The test parameters were ISO 179-1, using a 21.6 J hammer dropped from an angle of 150.0°.

[0111] Tensile test of cured film Films of the cured compositions were prepared by combining 40 g of sample formulation with 4 g of accelerator from SCOTCH-WELD DP8410NS acrylic adhesive (3M Company) in a polypropylene Max100 DAC cup (FlackTek, Inc., Landrum, SC, part number 501 221). The cup was sealed with a polypropylene lid, and the mixture was high-shear mixed at 1500 rpm (revolutions per minute) for 25 seconds at ambient temperature and pressure using a FlackTek, Inc. SPEEDEMIXER (DAC 400.2 VAC). The resulting mixture was coated between silicone-treated polyester release liners to a thickness of approximately 1 mm. The coated film was allowed to rest at room temperature for a minimum of 24 hours before testing. Tensile elongation measurements were performed according to ASTM standard D638-14 "Standard Test Method for Tensile Properties of Plastics" 2015, using a TYPE-V die for specimen cutting and a crosshead test speed of 100 mm / min.

[0112] Dynamic Mechanical Analysis ("DMA") Testing Film samples were prepared using the films prepared for tensile testing as described above. Film samples were cut to approximately 6-7 mm wide x 1 mm thick x 50 mm long and tested in a DMAQ800 (TA Instruments Inc., New Castle, DE) using a dual cantilever fixture with the following settings: frequency = 1 Hz, oscillation amplitude = 15 μm, and minimum oscillation force = 0.02 N. Film samples were equilibrated to -75°C and held at that temperature for 5 minutes, followed by a temperature ramp of 3.0°C / min to 150°C.

[0113] Preparation Example 1: Preparation of methacryloxyurea-terminated branched diamine poly(tetrahydrofuran) ("HC-1101 / IEM") DYNAMAR HC-1101 ("HC-1101") was heated at 65°C to melt the solid material and reduce the viscosity. The molten HC-1101 (245.0 g) was charged to a three-neck round-bottom flask equipped with a distillation head, thermocouple, and overhead stirrer. The flask was sparged with nitrogen and heated to 70°C. To the very viscous heated HC-1101, methyl ethyl ketone (60 mL) was added with stirring. An equal amount of methyl ethyl ketone was then distilled off under vacuum to obtain dry HC-1101. To the dry HC-1101, 2-isocyanatoethyl methacrylate ("IEM") (5.32 g) was added dropwise under nitrogen, and stirring was continued at 70°C for 16 hours. Isocyanate consumption was monitored by transmission FTIR spectroscopy. The resulting material was discharged at 70° C. to give 196.2 g (78% yield) of a viscous, pale yellow oil, HC-1101 / IEM, which solidified upon cooling to ambient temperature.

[0114] Preparation Example 2: Preparation of methacrylate-functional pure primary poly(tetramethylene oxide) diamines ("PPDA-6K / IEM" and "PPDA-9K / IEM") [ka] [Table 2] Linear polytetrahydrofuran diamine PPDA-6K (122.5 g), prepared as described in U.S. Patent No. 4,833,213 (Leir, et al.), was added to a 500 mL resin flask equipped with a thermocouple, a stainless steel mechanical stirrer, and a vacuum adapter. The flask was heated to 75°C and kept under high vacuum overnight (14 hours). The flask was refilled with dry air and PROSTAB 5198 (44.0 mg) was added. Mix well and the flask was cooled to 50°C. The heat source was removed. 2-Isocyanatoethyl methacrylate (6.42 g) was added and stirred well. As the 2-isocyanatoethyl methacrylate was mixed, the clear viscous oil became opaque. After 30 minutes, all of the isocyanate was consumed, as evidenced by transmission FTIR analysis. The material was removed to yield 125.8 g (98% yield) of an opaque viscous oil, which solidified upon cooling.

[0115] [Table 3] Linear polytetrahydrofuran diamine PPDA-9K (82.07 g), prepared as described in U.S. Patent No. 4,833,213 (Leir, et al.), was added to a 500 mL resin flask equipped with a thermocouple, a stainless steel mechanical stirrer, and a vacuum adapter. The flask was heated to 75°C and kept under high vacuum overnight (16 hours). The flask was refilled with dry air and PROSTAB 5198 (23.3 mg) was added. Mix well and the flask was cooled to 50°C. The mixture was removed from the heat source. 2-Isocyanatoethyl methacrylate (2.85 g) was added and stirred well. After 30 minutes, all of the isocyanate was consumed, as evidenced by transmission FTIR analysis. The material was discharged to give 80.0 g (94% yield) of a viscous, pale yellow oil, which solidified upon cooling.

[0116] Preparation Example 3: Synthesis of methacryloxyurea-terminated silicone methacrylate ("MAUS-1K / IEM," "MAUS-5K / IEM," and "MAUS-25K / IEM") crosslinkers [ka] [Table 4] For each material, silicone diamine and 2-isocyanatoethyl methacrylate ("IEM") are added to a polypropylene MAX 200 DAC cup (FlackTek, Inc., Landrum, SC, part number 501 220p-j) in the amounts listed in Table 4. The cup is sealed with a polypropylene lid, and the mixture is high-shear mixed at ambient temperature and pressure using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC) at 2000 rpm for 1 minute. After mixing, the mixture will be warm as a result of an exothermic reaction. The mixture is allowed to react under ambient conditions for at least 24 hours before use.

[0117] Preparative Example 4: Synthesis of methacrylate-functional poly(tetramethylene oxide) diols ("THF 2000 / IEM" and "THF 2900 / IEM") [ka] Poly(tetramethylene oxide) diols of two molecular weights, 2000 g / mol and 2900 g / mol, were used to prepare methacrylate-functional poly(tetramethylene oxide) diols using the following procedure. [Table 5]

[0118] The diol is heated to 70°C to melt. The amount of molten diol listed in Table 5 is transferred to a polypropylene MAX 200 DAC cup (FlackTek, Inc., Landrum, SC, part number 501 220p-j) (separate cup for each diol), followed by the amount of isocyanatoethyl methacrylate ("IEM") listed in Table 5. The cup is sealed with a polypropylene lid, and the mixture is high-shear mixed at 2000 rpm for 1 minute using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC) at ambient temperature and pressure. The sealed container is maintained at 60°C in an oven. The reaction mixture is monitored over time using attenuated total reflectance ("ATR") FTIR spectroscopy. The total reaction time is 17 hours, after which time the ATR indicates a peak at approximately 2264 cm. -1 Isocyanate-NCO peak at 3500 cm -1 The disappearance of the OH peak at 3400 cm -1 This shows the appearance of an NH peak at 100°C, confirming that the reaction is complete.

[0119] Preparative Example 5: Synthesis of methacrylate-functional PLACCEL H1P ("PCL H1P / IEM") Using the procedure described above for poly(tetramethylene oxide) diol, a 10,000 molecular weight poly(caprolactone) diol is methacrylate functionalized, where PLACCEL H1P (200 g) is combined with 2-isocyanatoethyl methacrylate (7.19 g) at 80° C. for 4 hours.

[0120] Preparative Example 6: Synthesis of methacrylate-functional D4000 ("D4000 / IEM") To a polypropylene MAX 200 DAC cup (FlackTek, Inc., Landrum, SC, part number 501 220 pj) was added 100 g of JEFFAMINE D4000, 7.8 g of 2-isocyanatoethyl methacrylate, and 0.25 g of MEHQ. The cup was sealed with a polypropylene lid, and the mixture was high-shear mixed at 2000 rpm for 1 minute using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC) at ambient temperature and pressure. After mixing, the mixture became warm as a result of an exothermic reaction. The methacrylate was allowed to react under ambient conditions for at least 24 hours before use.

[0121] Preparative Example 7: Synthesis of methacrylate-functional EC311 ("EC311 / IEM") To a polypropylene MAX 200 DAC cup (FlackTek, Inc., Landrum, SC, part number 501 220 pj) was added EC311 (100 g), 2-isocyanatoethyl methacrylate (8.0 g), and MEHQ (0.25 g). The cup was sealed with a polypropylene lid, and the mixture was high-shear mixed at ambient temperature and pressure using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC) at 2000 rpm for 1 minute. After mixing, the mixture became warm as a result of an exothermic reaction. The methacrylate was allowed to react under ambient conditions for at least 24 hours before use.

[0122] Preparation Example 8: Synthesis of methacrylate-functional polyfarnesenediol ("F3000 / IEM") Poly(farnesene) F3000 (100 g) and 2-isocyanatoethyl methacrylate (11.4 g) are added to a polypropylene MAX 200 DAC cup (FlackTek, Inc., Landrum, SC, part number 501 220 pj). The cup is sealed with a polypropylene lid, and the mixture is high-shear mixed at 2000 rpm for 1 minute using a FlackTek, Inc. SPEEDMIXER (DAC 400.2 VAC) at ambient temperature and pressure. The sealed container is maintained at 70°C in an oven. The reaction mixture is monitored over time using attenuated total reflectance ("ATR") FTIR spectroscopy. The total reaction time is 7 hours, after which time the ATR indicates a peak at approximately 2264 cm. -1 Isocyanate-NCO peak at 3500 cm -1 The disappearance of the OH peak at 3400 cm -1 This shows the appearance of an NH peak at 100°C, confirming that the reaction is complete.

[0123] Example 1. Preparation of Curable Samples 1-15: Curable Samples 1-15 were prepared by combining the ingredients in Table 6 in polypropylene MAX 200 DAC cups (FlackTek, Inc., part number 501 220). Curable Samples 1-15 differ based on the identity of the methacrylate crosslinker, which is listed in Table 7. After capping with a polypropylene lid, the mixtures were mixed three times for 1 minute at 1500 rpm in a speed mixer (FlackTek, Inc., DAC 400.2 VAC), with manual stirring using a wooden tongue depressor between mixes. The samples were degassed by capping with a vented polypropylene lid and high-shear mixing under vacuum (35 Torr). Curable samples containing methyl methacrylate crosslinker were stored refrigerated (approximately 6°C) until use. [Table 6] [Table 7]

[0124] Example 2. Preparation of curable samples 16-19: Curable Samples 16-19 were prepared by following the procedure described above for the preparation of Curable Samples 1-15, except using the ingredients listed in Table 8. [Table 8]

[0125] Example 3. Preparation of curable samples 20-22: Curable Samples 20-22 were prepared by following the procedure described above for the preparation of Curable Samples 1-15, except using the ingredients listed in Table 9. [Table 9]

[0126] Example 4: Testing of sample films and composites Using the procedures described above, film coatings incorporating the samples in Tables 7-10 were prepared. Test procedures for tensile elongation measurements and dynamic mechanical analysis ("DMA") using the prepared film coatings are described above. Test results for the sample films are shown in Tables 10 and 11 below. [Table 10] [Table 11]

[0127] Using the procedures described above, bonds were prepared incorporating the samples in Tables 7-10 between aluminum coupons. Procedures for overlap shear and impact testing are described above, and test results are shown in Tables 12 and 13 below. [Table 12] [Table 13]

[0128] The data in Tables 10-13 show that sample formulations containing crosslinkers of the present disclosure can result in adhesives with elongations of over 400% while still maintaining good structural adhesion and impact resistance.

[0129] It has surprisingly been found that formulations with very high elongation, approximately 400% or greater, exhibit stretch delamination, which can allow for rework of parts bonded with these adhesives. Materials with elongation values ​​less than 400% tend to break when stretched. Furthermore, adhesives with both low modulus and high elongation can desirably provide low bondline sink when used to bond materials together.

[0130] Example 5. Aging Test of Glass / Glass Overlaid Sheet ("OLS") Ten sides of a 10:1 dual syringe cartridge dispenser were loaded with sample formulation 21, prepared as described above, and one side of the dispenser was used with an accelerator from 3M SCOTCH-WELD DP8410NS acrylic adhesive (3M Company). All bonds were prepared by dispensing the adhesive composition and accelerator through a static mixing tip. The adhesive was used to prepare overlap shear aging test specimens on glass substrates that had been prepared by wiping with isopropanol. Overlap shear specimens with a 0.5 inch (1.27 cm) overlap were prepared on glass coupons (1 / 4 inch (0.635 mm) thick x 1 inch (25.4 mm) wide x 4 inches (101.6 mm) long). The bondline was clamped with binder clips during cure and the clips were removed after 24 hours at 25°C. Control glass test samples 1 and 2 were conditioned at 77°F (25°C) and 50% relative humidity and measurements were taken for overlap shear at 3 weeks with a 5000 lb (22 kN) load cell ("OLS Aging Results"). Glass test samples 3-8 were conditioned at 150°F (66°C) and 85% relative humidity and measurements were taken for overlap shear at 1 week, 2 weeks, and 3 weeks with a 5000 lb (22 kN) load cell. Values ​​are the average of three test specimens. The data are shown in Table 14. [Table 14]

[0131] It was expected that methacrylate monomer-based adhesives, such as those prepared with Sample Formulation 21, would hydrolyze upon heat / humidity aging, i.e., at 150°F (66°C) and 85% relative humidity, and therefore would experience a decrease in OLS values ​​as aging continued. Surprisingly, the data in Table 14 show that the adhesive prepared using Sample Formulation 21 did not behave in this manner, suggesting that adhesive formulations of the present disclosure may have utility as sealants.

[0132] Example 6. Plastic / Plastic Overlap Shear Test Ten sides of a 10:1 dual syringe cartridge dispenser were loaded with Sample 22, prepared as described above, and one side of the dispenser was loaded with an accelerator from 3M SCOTCH-WELD DP8410NS acrylic adhesive (3M Company). Three commercially available acrylic adhesives were also evaluated: 3M SCOTCH-WELD DP8410NS, 3M SCOTCH-WELD DP8010 Blue, and 3M SCOTCH-WELD DP8805 Green (all from 3M Company). For each formulation, bonds were prepared by dispensing the adhesive composition and accelerator through a static mixing tip. The adhesives were used to prepare 0.5-inch (1.27 cm) overlap shear test specimens on nylon 6,6 substrates (0.318 cm x 2.54 cm x 10.16 cm) from Plastics International (Eden Prairie, MN), which had been wiped and prepared with isopropanol. For Sample 22, glass spacer beads (76 micrometers to 127 micrometers) were applied to the adhesive to ensure uniform bondline thickness. Three 0.5 inch (1.27 cm) overlap shear test specimens were prepared for each adhesive formulation by applying two small binder clips (Model 10667CT from Staples Inc., Framingham, MA) to each specimen to hold the substrate in place. After 24 hours at 25°C, the clips were removed and the overlap shear test was performed as described above using a grip speed of 2.0 inches (5.08 cm) per minute, and the data was recorded as the average of three values, as shown in Table 14 below. [Table 15]

[0133] Most commercially available epoxy, polyurethane, and acrylic adhesives (and their composites) are unable to bond to nylon / polyamide substrates with "structural" bond strengths (i.e., greater than 1000 psi in a typical lap shear test). This is especially true if the substrates are not subjected to surface treatment (e.g., corona, flame, sanding) prior to bonding. However, as the data in Table 15 demonstrate, Sample 22 adhesive, which includes a crosslinker of the present disclosure, exhibits surprisingly high bond strengths (i.e., 1402 psi) when bonded to a nylon 6,6 substrate without any surface treatment.

[0134] Examples 7-9. Bonding (and debonding) of glass to aluminum panels [Table 16] The 10-part of a 10:1 dual syringe cartridge dispenser was loaded with Examples 7, 8, and 9 described above, using an accelerator from SCOTCH-WELD D8410NS acrylic adhesive (3M Company). This adhesive was used to bond a 152.4 mm x 101.6 mm x 0.8 mm aluminum panel (available from ACT Test Panels, Hillsdale, MI) to a 152.4 mm x 76.2 mm x 0.7 mm thick borosilicate glass (Eagle XG, Swift Glass, New York) for Example 7, or to a 158 mm x 77 mm x 0.7 mm "CORNING GORILLA" glass (Corning, Inc., Corning, New York) for Examples 8 and 9. Two layers of vinyl tape (Vinyl tape 471, 3M Company) were used to control the adhesive bead height to 0.25 mm. Using an automated dispensing device available from NuStar Instruments (Suzhou New Star Precision Machinery Co., Suzhou, China), the adhesive was dispensed onto the aluminum panel, with the adhesive bead spaced 4 mm from the outer edge of the glass. The volume of the adhesive bead was controlled to achieve a width of 1.0 mm after bonding. After the bead was dispensed onto the aluminum panel, the glass panel was carefully placed on top of it, tape-side down, and 1 kg weights were then placed near the top and bottom edges of the panel to maintain contact between the panels at the tape interface and ensure a 0.25 mm adhesive bondline gap. The adhesive was allowed to cure at room temperature for at least 72 hours, resulting in the glass adhesively bonded to the aluminum panel, after which the weights were removed.

[0135] The samples, including Example 7, were then placed on a hot plate set at 65°C to effect peeling. After 3 minutes, the backside of a thin razor blade was used to reveal a small tab of the adhesive bead. Tweezers were then used to pull the tab outward from the aluminum and glass sandwich at an approximately 90° angle to the adhesive bead. The adhesive stretched and peeled cleanly from the bondline, removing in a single piece without breaking during removal. By "cleanly peeled," we mean that there was essentially no visible adhesive residue on either surface after the adhesive was pulled away from the substrate.

[0136] Glass bonded to aluminum substrates using the compositions of Examples 8 and 9 was placed on a hot plate set at 65°C and secured with tape. After heating the bonded substrates for several minutes, a piece of Oral B Glide dental floss (Proctor & Gamble Company, Cincinnati, Ohio) was inserted into one of the bonded corners. The floss was then pulled through the entire bonded area, and the glass was easily removed. At this time, the adhesive residue peeled off cleanly in long strands.

[0137] The adhesives of the present disclosure have elongation at high temperatures and a low modulus, allowing for separation of parts by heat and non-wire strings, while the high elongation allows for easy removal of residual adhesive.

[0138] All references, patent documents and patent applications cited in the above patent application are incorporated herein by reference in their entirety for consistency. In the event of any inconsistency or contradiction between any of the incorporated references and this application, the information in the foregoing description shall prevail. The foregoing description is intended to enable a person skilled in the art to practice the disclosure as set forth in the claims, and should not be construed as limiting the scope of the present disclosure, which is defined by the claims and all equivalents thereof.

Claims

1. Formula LR １ ｑ A compound represented by: [In the formula, Each R １ are independently a functional group represented by the formula: 【Chemistry 1】 (In the formula, Each R ２ are independently hydrogen or methyl; n is an integer from 1 to 5, inclusive; X is O, S, or NH; Y is a single bond or a divalent group represented by the formula: 【Chemistry 2】 (In the formula, N' is R １ is the nitrogen bonded to the carbonyl carbon of T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof. is selected from q is an integer of 2 or more, L is a monomer unit a represented by the following formula: 【Transformation 3】 (In the formula, R ３ is hydrogen or a Z-terminal alkyl or heteroalkylene chain, wherein each Z-terminal chain may independently comprise a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and each Z is independently O or NH; and Monomer unit b represented by the following formula: 【Chemistry 4】 (wherein n is an integer from 1 to 5 (inclusive), and each R ４ is independently hydrogen or alkyl, and each Z is independently O or NH. is a q-valent organic polymer comprising A crosslinking agent comprising:

2. 2. The crosslinker of claim 1, wherein the q-valent organic polymer L has a number average molecular weight of 4,000 grams / mole to 54,000 grams / mole relative to polystyrene standards.

3. monofunctional monomers, a curing initiator system, and Formula LR １ ｑ A compound represented by: [In the formula, Each R １ are independently a functional group represented by the formula: 【Transformation 5】 (In the formula, Each R ２ are independently hydrogen or methyl; n is an integer from 1 to 5, inclusive; X is O, S, or NH; Y is a single bond or a divalent group represented by the formula: 【Transformation 6】 (In the formula, N' is R １ is the nitrogen bonded to the carbonyl carbon of T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof. is selected from q is an integer of 2 or more, L has a number average molecular weight of 4000 g / mole to 54000 g / mole relative to polystyrene standards and is represented by the following formula: 【Transformation 7】 (In the formula, R ３ is hydrogen or a Z-terminal alkyl or heteroalkylene chain, wherein each Z-terminal chain may independently comprise a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and each Z is independently O or NH; and Monomer unit b represented by the following formula: 【Transformation 8】 wherein n is an integer from 1 to 5 (inclusive), each R 4 is independently hydrogen or alkyl, and each Z is independently O or NH. is a q-valent organic polymer comprising 1. A curable composition comprising:

4. 4. The curable composition of claim 3, wherein the monofunctional monomer is selected from the group consisting of methyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid, 2-(2-butoxyethoxy)ethyl methacrylate, glycerol formal methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, and combinations thereof.

5. The q-valent organic polymer L is represented by the formula 【Chemistry 12】 [In the formula, each R ６ are independently hydrogen, a monomeric unit selected from the group consisting of monomeric units a) and b), or a Z-terminal alkyl chain, wherein said Z-terminal alkyl chain optionally comprises a linkage selected from the group consisting of a secondary amino linkage, a tertiary amino linkage, an ether linkage, and combinations thereof, and Z is O or NH.

5. The curable composition of claim 3 or 4, further comprising a monomer unit selected from the group consisting of monomer units represented by:

6. The q-valent organic polymer L is represented by the formula 【Chemistry 13】 wherein T is a divalent group selected from the group consisting of linear alkylene, cyclic alkylene, unsubstituted arylene, substituted arylene, and combinations thereof. The curable composition according to any one of claims 3 to 5, further comprising a monomer unit represented by:

7. 7. The curable composition of any one of claims 3 to 6, further comprising a filler selected from the group consisting of microfibrillated polyethylene, fumed silica, talc, wollastonite, aluminosilicate clay, phlogopite mica, calcium carbonate, kaolin clay, and combinations thereof.

8. 8. An elastomeric article prepared from at least one of the crosslinking agents of claim 1 or 2 or the curable compositions of any one of claims 3 to 7, wherein the elastomeric article has a minimum ultimate elongation of at least 50%.

9. A bonded article comprising the elastomeric article of claim 8 bonded to a substrate.

10. 10. A method of debonding a first substrate bonded to a second substrate by a bead of the elastomeric product of claim 8, comprising: detaching the beads from at least one of the first substrate or the second substrate, wherein the beads stretch-detach from at least one of the first substrate or the second substrate.

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