Two-component polyurethane adhesive composition

Abstract

Provided herein are two-part polyurethane adhesive compositions.

Description

[Technical field]

[0001] The present invention relates to the field of two-part polyurethane adhesive compositions. [Background technology]

[0002] Two-part polyurethane (PU) adhesives or sealants are used extensively in the automotive industry, either in repair or assembly plants, to bond painted or e-coated metal panels, painted or surface-treated plastics or composites. The adhesive or sealant chemistry commonly used on the market today is the isocyanate-containing polyurethane technology.

[0003] A conventional two-part PU adhesive consists of part A, which contains an isocyanate-terminated PU polymer (blocked or unblocked), and part B, which contains a polyamine. During use, parts A and B are mixed, which initiates curing by reaction of the amine and isocyanate groups.

[0004] The disadvantage of such adhesives is that they contain residual diisocyanate monomers that are considered toxic. New regulations require that the residual diisocyanate content be less than 0.1%, otherwise users need to be specially trained (https: / / echa.europa.eu / registry-of-restriction-intentions / - / dislist / details / 0b0236e180876053).

[0005] One way to reduce the monomeric diisocyanate content is to remove the excess monomer by distillation, but this process is expensive, time- and energy-consuming and therefore not preferred.To eliminate the potential risk, it would be preferable to formulate the 2K PU adhesive in the absence of isocyanates. Summary of the Invention [Means for solving the problem]

[0006] In a first aspect, the present invention provides a method for producing a composition comprising the steps of: (A) reacting at least one polyisocyanate with at least one polyol (resulting in intermediate I), and then reacting the resulting intermediate with a polyisocyanate having the formula I:

[0007] [ka]

[0008] (Wherein, R1 and R 2 is independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C 1 ~C6 alkyl) a polyurethane prepolymer produced by reacting molecules of and optionally a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I. Includes wherein the molecule of formula I is used in an amount that will react with all of the NCO groups in intermediate I as well as any residual monomeric isocyanates. Component A; (B) Component B comprising a polyamine and, optionally, a catalyst capable of catalyzing the reaction of the amine with a moiety derived from a molecule of Formula I; A two-component polyurethane adhesive composition comprising: At least one of component A and component B comprises a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I, and component A has an NCO content of less than 0.1 wt. %, as measured in accordance with ASTM D2572-97; An adhesive composition is provided.

[0009] In a second aspect, the present invention provides a method for producing a composition comprising the steps of: (1) reacting at least one polyisocyanate with at least one polyol to produce intermediate I; (2) Formula I:

[0010] [ka]

[0011] (Wherein, R1 and R 2 is independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C 1 ~C6 alkyl) reacting with a molecule of A method for producing a polyurethane prepolymer, comprising: The molecule of formula I is used in an amount sufficient to react with all of the NCO groups of intermediate I and with residual monomeric polyisocyanates to provide an NCO content of less than 0.1 weight percent as measured according to ASTM D2572-97. A method of manufacture is provided.

[0012] In a third aspect, the present invention provides a method for bonding a first substrate to a second substrate, the method comprising the steps of: (1) mixing component A and component B of the adhesive composition of the present invention to obtain a mixture; (2) applying the mixture to a first substrate, a second substrate, or both; (3) bringing the first substrate into adhesive contact with the second substrate; (4) Curing the mixture The present invention provides a bonding method comprising the steps of:

[0013] In a fourth aspect, the present invention provides a method for producing a composition comprising the steps of: (1) a first substrate; (2) a second substrate; (3) The adhesive composition according to the present invention, obtained by mixing component A and component B. An adhesive assembly comprising: a first and a second substrate being in adhesive contact with the adhesive composition sandwiched therebetween; An adhesive assembly is provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] We have found that it is possible to essentially eliminate monomeric isocyanate contamination as well as isocyanate groups in adhesives using the techniques of the present invention.

[0015] Definitions and Abbreviations MDI 4,4'-methylenebis(phenylisocyanate) HDI Hexamethylene Diisocyanate IPDI Isophorone Diisocyanate PU Polyurethane SEC Size Exclusion Chromatography RH Relative Humidity

[0016] The equivalent weight and molecular weight were determined by gel permeation chromatography (GPC) using a Malvern Viscothek GPC max instrument. Tetrahydrofuran (THF) was used as the eluent, PL GEL MIXED D (Agilent, 300*7.5mm, 5μm) was used as the column, and MALVERN Viscotek TDA (integrated refractive index viscometer and light scattering) was used as the detector.

[0017] Ingredient A Component A comprises a polyurethane prepolymer prepared by reacting at least one polyisocyanate with at least one polyol (to yield intermediate I), followed by reaction with a molecule of formula I.

[0018] Polyisocyanates and polyols The compositions of the present invention comprise a polyurethane prepolymer prepared by reacting at least one polyisocyanate with at least one polyol (to yield intermediate I), and then reacting with at least one molecule of formula I in an amount to react all of the NCO groups.

[0019] The at least one polyol is preferably selected from polyether polyols, polyester polyols (e.g., polycaprolactone), polybutadiene diols, polycarbonate diols, aliphatic diols (polyols), and mixtures of any of these. Polyether polyols are particularly preferred.

[0020] The at least one polyol is preferably a diol, triol or tetraol. Preferably, it is a triol or a mixture of triols and diols, with triols being particularly preferred.

[0021] Polyether polyols useful in the present invention include, for example, polyether polyols, poly(alkylene carbonate) polyols, hydroxyl-containing polythioethers, polymer polyols, and mixtures thereof. Polyether polyols are well known in the art and include, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, and polytetramethylene ether diols and triols, which can be prepared, for example, by reacting unsubstituted or halogen- or aromatic-substituted ethylene oxide or propylene oxide with an initiator compound containing two or more active hydrogen groups, such as water, ammonia, polyhydric alcohol, or amine. In general, polyether polyols can be prepared by polymerizing alkylene oxides in the presence of active hydrogen-containing initiator compounds. Preferred polyether polyols contain one or more alkylene oxide units in the polyol backbone. Preferred alkylene oxide units are ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. Preferably, the polyol contains propylene oxide units, ethylene oxide units or mixtures thereof. In embodiments in which a mixture of alkylene oxide units is contained in the polyol, the different units can be arranged randomly or in blocks of each alkylene oxide. In a preferred embodiment, the polyol comprises propylene oxide chains. In a preferred embodiment, the polyether polyol is a mixture of polyether diols and polyether triols. Preferably, the polyether polyol or mixture has a functionality of at least about 2.0; preferably about 3.0 or more, e.g., 3.5, 4.0 or more. Preferably, the equivalent weight of the polyether polyol mixture is at least about 200 Da, more preferably at least about 500 Da, more preferably at least about 1,000 Da; preferably about 5,000 Da or less, more preferably about 3,000 Da or less.

[0022] More specific examples of polyether polyols include the following: 1. Difunctional polyols (diols), such as poly(alkylene oxide) diols, in which the alkylene groups are C2 to C4, in particular poly(propylene oxide) diols, such as poly(ethylene oxide) diol, poly(propylene oxide) diol, poly(butylene oxide) diol and poly(tetramethylene oxide) diol, are particularly preferred. In a particularly preferred embodiment, the polyether polyol comprises a nominally difunctional poly(propylene oxide) having an equivalent weight of 100 to 10,000, more preferably 500 to 3,000, and particularly preferably 1,000 to 2,000. 2. Trifunctional polyols (triols), for example alkylene oxides initiated with trifunctional polyols such as trimethylolpropane, in which the alkylene groups are C2 to C4, are particularly preferred, especially those based on ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide and butylene oxide, with propylene oxide being particularly preferred. In a particularly preferred embodiment, the polyether polyol comprises a nominally trifunctional poly(propylene oxide) having an equivalent weight of 100 to 10,000, more preferably 500 to 3,000, and especially preferably 1,000 to 2,000; the polymer may or may not be capped with ethylene oxide to modify its reactivity. 3. Mixtures of 1 and 2. Mixtures of 1 and 2 are particularly preferred, with mixtures of a) a nominally difunctional poly(propylene oxide) having an equivalent weight of 100 to 10,000, more preferably 500 to 3,000, and especially preferably 1,000 to 2,000, and b) a nominally trifunctional poly(propylene oxide) having an equivalent weight of 1,000 to 2,000, especially in a weight ratio b) / a) of 0:1 to 2:1 being more particularly preferred.

[0023] In a particularly preferred embodiment, the at least one polyol comprises a propylene oxide-based diol or triol. Preferably, the polypropylene oxide-based diol or triol has a molecular weight of 1,000 to 5,000 Da, more preferably 1,000 to 3,000 Da. In a preferred embodiment, the at least one polyol comprises a polypropylene oxide-based diol having a molecular weight of 1,000 to 5,000 Da, more preferably 1,000 to 3,000 Da.

[0024] Polyester polyols include any hydroxyl-terminated polyester. Particularly preferred are hydroxyl-terminated aliphatic polyesters and polycaprolactones. Particularly preferred are polyester diols and triols, especially polyester triols. Particularly preferred are copolyesters having a molecular weight of 2,000 to 4,000 Da, preferably 3,500 Da.

[0025] There is no particular limitation on the polyisocyanates that can be used to prepare intermediate I. Diisocyanates are preferred.

[0026] Aliphatic and aromatic diisocyanates may be used, with aliphatic being preferred. Examples of suitable diisocyanates include toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene biscyclohexyl isocyanate (HMDI) (hydrogenated MDI), MDI (especially 4,4'- and 4,2-MDI) and isophorone diisocyanate (IPDI), with HDI being particularly preferred.

[0027] In a preferred embodiment, intermediate I is prepared by reacting a polyether triol with HDI. In a particularly preferred embodiment, it is prepared by reacting a polypropylene oxide-based triol with HDI. In a more particularly preferred embodiment, it is prepared by reacting a polypropylene oxide-based triol of molecular weight 4,800 with HDI.

[0028] In a preferred embodiment, intermediate I is prepared by reacting an aliphatic polyester having a molecular weight of 3,500 with MDI. In a particularly preferred embodiment, the polyester prepolymer is prepared by reacting 65-80% by weight of a polyester diol with 5-15% by weight of MDI.

[0029] Intermediate I may comprise a mixture of a polyether polyol-based prepolymer and a polyester-based prepolymer.

[0030] In a particularly preferred embodiment, intermediate I is based on polyether diols and polyether triols.

[0031] The diisocyanate that can be used to prepare intermediate I is not particularly limited. Aliphatic and aromatic diisocyanates can be used. Examples of suitable diisocyanates include toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene biscyclohexyl isocyanate (HMDI) (hydrogenated MDI), MDI (especially 4,4'- and 4,2-MDI) and isophorone diisocyanate (IPDI), with HDI being particularly preferred.

[0032] In particularly preferred embodiments, intermediate I comprises nominally trifunctional poly(propylene oxide) and nominally trifunctional poly(propylene oxide) reacted with MDI or HDI.

[0033] In a particularly preferred embodiment, intermediate I comprises a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000), and a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558) reacted with MDI or HDI.

[0034] Intermediate I is prepared by reacting at least one polyol with a polyisocyanate using a catalyst capable of catalyzing the reaction of NCO groups with hydroxyl groups. Preferred catalysts are listed below.

[0035] The polymerization may be carried out in the presence of a plasticizer, such as a high-boiling ester or diester, such as diisononyl phthalate, with diisononyl phthalate being particularly preferred.

[0036] In a preferred embodiment, intermediate I comprises, based on the total weight of intermediate I, 18 to 30% by weight, more preferably 19 to 25% by weight, and more particularly preferably 22 to 23% by weight of polyol diol.

[0037] In a preferred embodiment, intermediate I comprises 40 to 90% by weight, 50 to 90% by weight, more particularly preferably 75 to 85% by weight of polyol triol, based on the total weight of intermediate I.

[0038] In a preferred embodiment, intermediate I comprises 5 to 15 wt.-%, more preferably 8 to 12 wt.-%, and more particularly preferably 8 to 10 wt.-%, of diisocyanate, based on the total weight of intermediate I.

[0039] In a particularly preferred embodiment, intermediate I comprises, based on the total weight of intermediate I, 22 to 23 weight percent polyol diol, 32 to 33 weight percent polyol triol, and 9 to 11 weight percent diisocyanate.

[0040] In a preferred embodiment, intermediate I comprises 18 to 30 wt. %, more preferably 19 to 25 wt. %, and more particularly preferably 22 to 23 wt. %, based on the total weight of intermediate I, of a nominally difunctional poly(propylene oxide) having a hydroxyl number of 56 (1000 equivalent weight).

[0041] In a preferred embodiment, intermediate I comprises 25 to 40 wt. %, 28 to 35 wt. %, and more particularly preferably 32 to 33 wt. %, based on the total weight of intermediate I, of a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558).

[0042] In a preferred embodiment, intermediate I contains 5 to 15% by weight, more preferably 8 to 12% by weight, and more particularly preferably 9 to 11% by weight, of MDI or HDI, based on the total weight of intermediate I.

[0043] In a particularly preferred embodiment, intermediate I comprises 22-23 wt. % of a nominally difunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000), 32-33 wt. % of a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558), and 9-11 wt. % MDI, based on the total weight of intermediate I.

[0044] In a particularly preferred embodiment, intermediate I comprises 22-23 weight percent of a nominally difunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000), 32-33 weight percent of a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558), and 9-11 weight percent MDI, based on the total weight of intermediate I, and has an isocyanate content of 1.25 weight percent, and a viscosity of 16,000 cps at 23° C. as measured according to the procedure described in U.S. Pat. No. 5,922,809, column 12, lines 38-49.

[0045] End Groups (Molecules of Formula I) The prepolymer is prepared by reacting at least one polyisocyanate with at least one polyol (to provide intermediate I) and then reacting the polyisocyanate with a polyol having the formula I:

[0046] [ka]

[0047] (Wherein, R1 and R2 is independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C 1 ~C6 alkyl) It is produced by reacting with a molecule of

[0048] Preferably, R1 and R2 are independently selected from H and C1-C4 alkyl, more preferably H and C1-C2 alkyl, and particularly preferably R 1 and R 2 is H.

[0049] Preferably, n is 1.

[0050] Preferably, R 3 is C1-C4 alkyl, more preferably R 3 is C1-C2 alkyl, and particularly preferably R 3 is ethyl.

[0051] In a particularly preferred embodiment, in the molecule of formula I, R 1 and R 2 is H, n is 1, and R 3 is ethyl [2-(ethoxycarbonyl)cyclopentanone, CPEE].

[0052] [ka]

[0053] The molecule of formula I reacts with the NCO groups of intermediate I. It is preferably used in an amount that will react with all the NCO groups of intermediate I, meaning an amount that is at least equivalent to the free NCO groups of intermediate I, or in an excess amount, for example 1, 1.1 or 1.2 equivalents.

[0054] To reduce or eliminate any monomeric diisocyanates in intermediate I, the amount or molecule of formula I added is calculated to react not only with the NCO groups of intermediate I, but also with any residual monomeric diisocyanates. This essentially eliminates all NCO groups, both in the prepolymer and in the free monomeric diisocyanates, leading to an NCO content of less than 0.1% by weight, preferably essentially 0% by weight.

[0055] Catalysts for polyurethane prepolymers Intermediate I is prepared by reacting at least one polyisocyanate with at least one polyol in the presence of a catalyst capable of catalyzing the reaction of NCO and OH functional groups.

[0056] Examples of such catalysts include tertiary amine catalysts, bismuth catalysts, alkyltin carboxylates, oxides and mercaptides.Specific examples include triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylethanolamine, and bis-(2-dimethylaminoethyl)ether, bismuth catalysts, dibutyltin dilaurate, stannous octoate, with bismuth catalysts being particularly preferred.

[0057] Zinc catalysts, especially zinc carboxylate catalysts, are preferred for the reaction with molecules of formula I. In a preferred embodiment, a mixture of zinc carboxylate and bismuth carboxylate is used.

[0058] When an organometallic catalyst is used, it is any organometallic catalyst that can catalyze the reaction between an isocyanate and a functional group having at least one reactive hydrogen. Examples include bismuth catalysts, metal carboxylates, such as tin carboxylates, zinc carboxylates, etc. Metal alkanoates include stannous octoate, bismuth octoate, or bismuth neodecanoate. Preferably, the at least one organometallic catalyst is a bismuth catalyst or an organotin catalyst. Examples include dibutyltin dilaurate, dimethyltin dineodecanoate, dimethyltin mercaptide, dimethyltin carboxylate, dimethyltin dioleate, dimethyltin dithioglycolate, dibutyltin mercaptide, dibutyltin bis(2-ethylhexylthioglycolate), dibutyltin sulfide, dioctyltin dithioglycolate, dioctyltin mercaptide, dioctyltin dioctoate, dioctyltin dineodecanoate, dioctyltin dilaurate. In a particularly preferred embodiment, it is a bismuth catalyst.

[0059] The catalyst is preferably used in an amount of 0.05 to 2% by weight, more preferably 0.1 to 1% by weight, based on the total weight of the adhesive composition.

[0060] In a preferred embodiment, the catalyst is a zinc and bismuth catalyst and is used at 0.05 to 0.3 weight percent, based on the total weight of the adhesive composition.

[0061] Polyurethane Prepolymer Contemplated herein are polyurethane prepolymers resulting from the reaction of intermediate I and molecules of formula I, as detailed above, and any combination of polyols, polyisocyanates, and molecules of formula I.

[0062] In a preferred embodiment, the polyurethane prepolymer comprises a polypropylene oxide based diol having a MWT of 2,000 Da, 1,6-HDI and CPEE.

[0063] In a particularly preferred embodiment, the polyurethane prepolymer comprises 70-90 wt. % of a polypropylene oxide-based diol having a MWT of 2,000 g / mol, 5-15 wt. % of 1,6-HDI, and 5-15 wt. % of CPEE.

[0064] In a particularly preferred embodiment, the polyurethane prepolymer comprises 74.57 wt.% of a polypropylene oxide-based diol having a MW of 2,000 g / mol, 12.57 wt.% of 1,6-HDI, and 12.36 wt.% of CPEE.

[0065] The polyurethane prepolymer is preferably present in component A of the adhesive in an amount of 40 to 80% by weight, based on the total weight of component A, more preferably 45 to 75% by weight, and more particularly preferably 55 to 70% by weight.

[0066] In a particularly preferred embodiment, component A of the adhesive composition of the present invention comprises 40 to 80 wt. %, more preferably 45 to 75 wt. %, and more particularly preferably 55 to 70 wt. %, based on the total weight of component A, of a polyurethane prepolymer comprising a nominally difunctional poly(propylene oxide) and a nominally trifunctional poly(propylene oxide) reacted with MDI and then reacted with a molecule of formula I.

[0067] Preferably, the prepolymer or prepolymer mixture has a viscosity of at least 6,000 centipoise or at least about 8,000 centipoise, and up to 30,000 centipoise or up to 20,000 centipoise. If the viscosity is too high, the final adhesive composition will be difficult to pump. If the viscosity is too low, the final adhesive composition will be too runny and will sag.

[0068] The prepolymer equivalent weight and molecular weight are measured by gel permeation chromatography (GPC) using a Malvern Viscothek GPC max instrument. Tetrahydrofuran (THF) was used as the eluent, PL GEL MIXED D (Agilent, 300*7.5mm, 5μm) was used as the column, and MALVERN Viscotek TDA (integrated refractive index viscometer and light scattering) was used as the detector.

[0069] The polyurethane prepolymer has an isocyanate content of less than 0.1% by weight, more preferably 0% by weight.

[0070] In another preferred embodiment, the polyurethane prepolymer has an isocyanate content of less than 0.1 wt%, more preferably 0 wt%, and a viscosity of 16,000 cps at 23° C. as measured according to the procedure described in U.S. Pat. No. 5,922,809, column 12, lines 38-49.

[0071] In a preferred embodiment, component A is at least one polyurethane prepolymer as described herein; and CaO Includes.

[0072] In a preferred embodiment, component A is at least one polyurethane prepolymer as described herein; and Aluminum oxide Includes.

[0073] In a preferred embodiment, component A is at least one polyurethane prepolymer as described herein; Aluminum oxide; and CaO Includes.

[0074] Component B Component B comprises a polyamine and, optionally, a catalyst capable of catalyzing the reaction of the amine with a moiety derived from the molecule of Formula I.

[0075] Polyamines Component B comprises at least one polyamine, preferably a diamine or triamine, or a mixture thereof.

[0076] Preferably, the polyamine has a molecular weight of at least 400 Da, more preferably at least 1,000 Da, more particularly preferably at least 2,000 Da. In a preferred embodiment, the polyamine has a molecular weight of 2,000 to 4,000 Da, more preferably about 3,000 Da.

[0077] Preferably, the amine group is a primary or secondary amine group, particularly preferably a primary amine group.

[0078] In a preferred embodiment, the polyamine is a diamine, triamine or a mixture thereof, where the diamine or triamine has a molecular weight of 2,000 to 4,000 Da.

[0079] In another preferred embodiment, the polyamine is a triamine having primary amine groups and having a molecular weight of 2,000 to 4,000 Da, more preferably 3,000 Da.

[0080] Examples of suitable compounds having primary and / or secondary amino groups include polyoxyalkylene polyamines having 2 or more amine groups per polyamine, 2 to 4 amine groups per polyamine, or 2 to 3 amine groups per polyamine. Polyether amines having 3 amine groups are particularly preferred.

[0081] The polyoxyalkylene polyamine may have a weight average molecular weight of at least 400 Da, more preferably at least 1,000 Da, and more particularly preferably at least 2,000 Da. In a preferred embodiment, the polyoxyalkylene polyamine has a molecular weight of 2,000 to 4,000 Da, more preferably about 3,000 Da. The polyoxyalkylene polyamine may have a weight average molecular weight of about 5,000 or less, or about 3,000 or less.

[0082] Exemplary polyoxyalkylene polyamines include the following: 1. Polyamines based on a propylene oxide polyether backbone. Examples include: A trifunctional primary amine having an average molecular weight of approximately 440. The amine group is located on a secondary carbon atom at the end of an aliphatic polyether chain:

[0083] [ka]

[0084] ;Polypropylene oxide diamine having a molecular weight of about 400:

[0085] [ka]

[0086] a difunctional, primary amine having an average molecular weight of about 2000. The primary amine group is located on a secondary carbon atom at the end of an aliphatic polyether chain:

[0087] [ka]

[0088] formula:

[0089] [ka]

[0090] of approximately 3000 molecular weight triamine formula:

[0091] [ka]

[0092] of approximately 5,000 g / mol of triamine. 2. Polyamines based primarily on a polyethylene oxide polyether backbone. Examples are those of the general formula:

[0093] [ka]

[0094] It is of the following. For example, a polyamine with y ≈ 9, (x + z) ≈ 3.6 and a molecular weight of 600 g / mol; a 900 g / mol molecular weight polyamine with y ≈ 12.5 and (x + z) ≈ 6; For example, a polyamine with y ≒ 39, (x + z) ≒ 6 and a molecular weight of 2,000 g / mol.

[0095] In a particularly preferred embodiment, the at least one polyamine has the formula:

[0096] [ka]

[0097] The triamine may comprise or consist of approximately 3000 molecular weight triamine.

[0098] Other suitable polyamines include polyamidoamines, which contain repeating branched subunits of amide and amine functionalities. For example, a suitable polyamidoamine can be initiated with ammonia or ethylenediamine, reacted by Michael addition with an acrylate ester (e.g., methyl acrylate), and then reacted with the ester functional group and a diamine (e.g., ethylenediamine, etc.). This results in a primary amine-terminated polyamine, which can be reacted again with a Michael addition reaction and then reacted again with a diamine. The first "cycle" is represented diagrammatically below using ethylenediamine and methyl acrylate:

[0099] [ka]

[0100] Other suitable polyamines include phenalkamines prepared by the Mannich reaction between cardanol, formaldehyde, and at least one polyamine.

[0101] In a preferred embodiment, component B is made from the following ingredients: at least one polyamine; and A catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I. Includes.

[0102] In another preferred embodiment, component B is a mixture of the following ingredients: at least one polyamine; a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I; and CaO Includes.

[0103] In another preferred embodiment, component B is a mixture of the following ingredients: at least one polyamine; a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I; CaO; and At least one phenolic antioxidant Includes.

[0104] Calcium oxide In a preferred embodiment, component A and / or component B comprises calcium oxide (CaO).

[0105] When used, CaO is preferably present in the final mixture resulting from mixing of components A and B in a concentration of 2 to 6% by weight, more preferably 3 to 5% by weight, and especially preferably about 3.5% by weight, based on the total weight of the mixture of components A and B.

[0106] The above mentioned concentrations can be achieved by the presence of CaO in either or both of component A and component B. The concentration of CaO to be used in either component A or B can be calculated from the mix ratio of A:B and the desired final concentration in the mixed adhesive.

[0107] In a preferred embodiment, CaO is present in component A at 3-6 wt.%, more preferably 5 wt.%, based on the total weight of component A, and CaO is present in component B at 1-3 wt.%, more preferably 2 wt.%, based on the total weight of component B, such that when components A and B are mixed in a 1:1 ratio, the CaO concentration in the final mixed adhesive is 2-4.5 wt.%, more preferably 3.5 wt.%, based on the total weight of the mixed adhesive.

[0108] In a preferred embodiment, the present invention comprises: (A) reacting at least one polyisocyanate with at least one polyol (resulting in intermediate I), and then reacting the resulting intermediate with a polyisocyanate having the formula I:

[0109] [ka]

[0110] (Wherein, R1 and R 2is independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C 1 ~C6 alkyl) a polyurethane prepolymer produced by reacting molecules of and optionally a catalyst capable of catalyzing the reaction of an amine with a moiety derived from the molecule of formula I, and optionally a component A comprising CaO; (B) a component B comprising a polyamine, and optionally a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I, and optionally CaO; A two-part polyurethane adhesive composition comprising: At least one of component A and component B comprises a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I, and at least one of component A and component B comprises CaO; An adhesive composition is provided. Preferably, the two-part polyurethane adhesive composition has an NCO content of less than 0.1 wt.% as measured according to ASTM D2572-97.

[0111] Antioxidants In a preferred embodiment, component A and / or component B comprises at least one antioxidant, in particular at least one phenolic antioxidant, preferably a hindered phenol antioxidant.

[0112] Typical examples are 4,6-bis(octylthiomethyl)-o-cresol (Irganox 1520L), pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (Irganox 1010), octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate] (Irganox 1076), N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) (Irganox 1098), 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4,6-triyl)tri-p-cresol (Irganox 1099). 1330), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Irganox 3114), ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (Irganox 245), benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester (Irganox 1135), 3,5-di-tert-butyl-4-hydroxycinnamic acid (Irganox 3125), hexamethylene bis(3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate) (Irganox 259), thiodiethylene bis[3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate] (Irganox 1035).

[0113] 4,6-bis(octylthiomethyl)-o-cresol (Irganox 1520L) is particularly preferred.

[0114] When used, the at least one phenolic antioxidant is present in the final mixture resulting from mixing of Components A and B in a concentration of 0.5 to 6% by weight, more preferably 1 to 3% by weight, and especially preferably about 2% by weight, based on the total weight of the mixture of Components A and B.

[0115] The above concentrations can be achieved by the presence of at least one phenolic antioxidant in either or both of component A and component B. The concentration of phenolic antioxidant to be used in either component A or B can be calculated from the mix ratio of A:B and the desired final concentration in the mixed adhesive.

[0116] In a preferred embodiment, the at least one phenolic antioxidant is present in only Component A or only Component B in an amount of 2 to 6% by weight, more preferably 4% by weight, based on the total weight of Component A or Component B, such that when Components A and B are mixed in a 1:1 ratio, the concentration of the phenolic antioxidant in the final mixed adhesive is 1 to 3% by weight, more preferably 2% by weight, based on the total weight of the mixed adhesive.

[0117] In a particularly preferred embodiment, 4,6-bis(octylthiomethyl)-o-cresol is used in component A and / or component B in an amount that results in a final concentration in the mixed adhesive of 1 to 3 wt. %, more preferably 2 wt. %, based on the total weight of the mixed adhesive.

[0118] In a particularly preferred embodiment, the final mixed adhesive resulting from mixing components A and B comprises CaO and a phenolic antioxidant, in particular a hindered phenolic antioxidant. Particularly preferably, the final mixed adhesive resulting from mixing components A and B comprises 2-4.5 wt. %, more preferably 3.5 wt. %, of CaO, and 1-3 wt. %, more preferably 2 wt. %, of the phenolic antioxidant, based on the total weight of the mixed adhesive.

[0119] In another preferred embodiment, the final mixed adhesive resulting from mixing components A and B comprises 2-4.5 wt. %, more preferably 3.5 wt. %, of CaO, and 1-3 wt. %, more preferably 2 wt. %, of 4,6-bis(octylthiomethyl)-o-cresol, based on the total weight of the mixed adhesive. In a particularly preferred embodiment, the final mixed adhesive resulting from mixing components A and B comprises 2-4.5 wt. % of CaO and 1-3 wt. % of 4,6-bis(octylthiomethyl)-o-cresol, based on the total weight of the mixed adhesive.

[0120] In a preferred embodiment, the present invention comprises: (A) reacting at least one polyisocyanate with at least one polyol (resulting in intermediate I), and then reacting the resulting intermediate with a polyisocyanate having the formula I:

[0121] [ka]

[0122] (Wherein, R1 and R 2 is independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C 1 ~C6 alkyl) a polyurethane prepolymer produced by reacting molecules of and optionally a catalyst capable of catalyzing the reaction of an amine with a moiety derived from the molecule of formula I, and optionally CaO, and optionally a phenolic antioxidant, component A; (B) a component B comprising a polyamine, and optionally a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I, and optionally CaO, and optionally a phenolic antioxidant; A two-part polyurethane adhesive composition comprising: at least one of component A and component B comprises a catalyst capable of catalyzing a reaction between an amine and a moiety derived from a molecule of formula I, at least one of component A and component B comprises CaO, and at least one of component A and component B comprises a phenolic antioxidant; An adhesive composition is provided. Preferably, the two-part polyurethane adhesive composition has an NCO content of less than 0.1 wt.% as measured according to ASTM D2572-97.

[0123] Method for producing polyurethane prepolymer The present invention relates to (1) reacting at least one polyisocyanate with at least one polyol to produce intermediate I; (2) Formula I:

[0124] [ka]

[0125] (Wherein, R1 and R 2 is independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C 1 ~C6 alkyl) reacting with a molecule of A method for producing a polyurethane prepolymer, comprising: The molecule of formula I is used in an amount sufficient to react with all of the NCO groups of intermediate I and with residual monomeric polyisocyanate to provide an NCO content of less than 0.1 weight percent as measured according to ASTM D2572-97; A method of manufacture is provided.

[0126] The amount of the molecule of formula I used can be calculated from the NCO content of intermediate I as measured according to ASTM D2572-97. Alternatively, the amount to be added can be theoretically calculated based on the amount of polyisocyanate used to make intermediate I. In a preferred embodiment, the molecule of formula I is used at 1.2 to 1.3 equivalents of the molecule of formula I with respect to the NCO content (both free NCO and NCO in the molecule of intermediate I).

[0127] An excess of polyisocyanate relative to polyol may be used, especially if it is desired to keep the molecular weight of intermediate I (and the polyurethane prepolymer made therefrom) low. Using conventional techniques, this results in residual monomeric polyisocyanate (NCO) in the prepolymer. The conventional method for removing monomeric NCO is by distillation, which is time consuming and energy consuming and is not practical for high molecular weight prepolymers.

[0128] The process of the invention essentially removes the NCO groups in the polyurethane prepolymer and the NCO groups of the residual monomers by reacting them with the molecule of formula I. This makes it possible to avoid distillation of the prepolymer.

[0129] In a preferred embodiment of the process of the present invention, intermediate I is prepared using a polyisocyanate in an amount of 1.2 equivalents or greater relative to the polyol.

[0130] An example of a method for producing a polyurethane prepolymer includes the following steps: 1. Stirring at least one polyol under an inert atmosphere (e.g., nitrogen or argon) or under vacuum, optionally in the presence of a plasticizer (e.g., diisononyl phthalate); 2. Adding at least one polyisocyanate; 3. adding a catalyst to yield intermediate I; 4. Once the desired NCO content is reached, adding a molecule of formula I in an amount sufficient to react with all of the NCO groups of intermediate I and the NCOs of any residual monomers. Includes.

[0131] A preferred embodiment of the method comprises the following steps: 1. Stirring at least one polyol under an inert atmosphere (e.g., nitrogen or argon), optionally in the presence of a plasticizer (e.g., diisononyl phthalate); 2. adding at least one polyisocyanate in an NCO:OH ratio of 1.5:1, 2:1, 4:1, 5:1 or greater; 3. adding a catalyst to yield intermediate I; 4. Once the desired NCO content is reached, adding the molecule of formula I in an NCO:formula I ratio of 1.2 to 1.5, preferably 1.2 to 1.3. Includes.

[0132] In a preferred embodiment, the method for producing a polyurethane prepolymer comprises the following steps: 1. Stirring at least one polyol under an inert atmosphere (e.g., nitrogen or argon) or under vacuum, and optionally in the presence of a plasticizer (e.g., diisononyl phthalate), heating to 65-150°C, then cooling to 60-80°C; 2. Adding at least one polyisocyanate; 3. Adding a catalyst and reacting the mixture at 60-100°C; 4. Once the desired NCO content is reached, cool the mixture of step 3 to 50-70° C. and add a molecule of formula I in an NCO:formula I ratio of 1.2-1.5, preferably 1.2-1.3. Includes.

[0133] Optional Ingredients The adhesive composition of the present invention may optionally contain a plasticizer, which may be present in component A or B or both. Examples of plasticizers are esters, especially diesters and triesters, particularly those having a viscosity of 10 at 23° C. -4Those having a vapor pressure of less than 1000 MPa. Examples include dialkyl phthalates, alkyl esters of fatty acids, phosphate esters (e.g. trioctyl phosphate, etc.). Diisononyl phthalate is particularly preferred. If used, the plasticizer is typically present at 10-20% by weight, preferably 12-18% by weight, based on the total weight of the adhesive composition. In a particularly preferred embodiment, diisononyl phthalate is used at 12-18% by weight, more preferably 16-17% by weight, based on the total weight of the adhesive composition.

[0134] The adhesive composition of the present invention may optionally contain fillers, which may be present in component A or B or both, such as carbon black, clays, carbonates (e.g. calcium carbonate), metal hydrates and fumed silica. Fillers are preferably used at 0-80 wt%, preferably 10-70, more preferably 20-60 wt%.

[0135] In a preferred embodiment, the adhesive of the present invention comprises clay as filler, preferably kaolin, in particular calcined kaolin. If used, the clay is used in an amount of 5 to 15% by weight, more preferably 8 to 12% by weight, based on the total weight of the adhesive composition. In a particularly preferred embodiment, the kaolin is used in an amount of 8 to 12% by weight, more preferably 9% by weight, based on the total weight of the adhesive composition.

[0136] In a preferred embodiment, the adhesive of the present invention comprises carbon black as a filler. The carbon black is not particularly limited. The preferred carbon black exhibits an oil absorption of dibutyl phthalate of at least 80, preferably at least 90, more preferably at least 95 cm3 per 100 g of carbon black, as measured according to ASTM D-2414-09. Furthermore, the carbon black desirably has an iodine value of at least 80, as measured according to ASTM D1510-11.

[0137] When used, carbon black is used in an amount of 5 to 30% by weight, more preferably 15 to 25% by weight, based on the total weight of the adhesive composition. In a particularly preferred embodiment, carbon black is used in an amount of 15 to 25% by weight, preferably 22 to 23% by weight, based on the total weight of the adhesive composition.

[0138] The adhesive composition of the present invention may optionally contain 0 to 20% by weight, more preferably 5 to 15% by weight, and particularly preferably 9 to 10% by weight, of calcium carbonate, based on the total weight of the adhesive composition. The calcium carbonate particles may be untreated or may be surface modified by treatment with chemicals, such as organic acids or esters of organic acids.

[0139] The adhesive composition of the present invention may optionally contain fumed silica at 0 to 1.5 wt %, more preferably 0.5 to 1 wt %, based on the total weight of the adhesive.

[0140] When fumed silica is used, the particles may be untreated or surface modified with chemicals such as chlorosilanes, dichlorosilanes, alkyltrialkoxysilanes, or polydimethylsiloxanes.

[0141] The adhesive composition of the present invention may optionally include talc, which may be present in Component A or B or both. In a preferred embodiment, talc is used in Component B at 25 to 40% by weight, more preferably 30 to 35% by weight, based on the total weight of Component B.

[0142] The adhesive composition of the present invention may optionally include an adhesion promoter, which may be present in component A or B or both. Suitable adhesion promoters include silanes such as gamma-glycidoxypropyltrimethoxysilane. In a preferred embodiment, gamma-glycidoxypropyltrimethoxysilane is used in component B at 0.5 to 2 wt %, preferably 1 wt %, based on the total weight of component B.

[0143] The adhesive composition of the present invention may optionally include a flame retardant and a synergist. Examples of suitable flame retardants and synergists include: 1. Aluminium, zinc and titanium salts of diethylphosphinic acid, in particular aluminium diethylphosphinate; 2. Nitrogen-containing and / or phosphorus-containing molecules, such as melamine polyphosphate, melamine pyrophosphate, melamine cyanurate, etc.; 3. Aluminum phosphite and / or zinc phosphite Examples include:

[0144] A preferred flame retardant / synergist combination is aluminum diethylphosphinate plus melamine polyphosphate.

[0145] The adhesive compositions of the present invention may optionally include one or more additional stabilizers, such as heat, visible light, and UV stabilizers.

[0146] Examples of heat stabilizers include alkyl-substituted phenols, phosphites, sebacates and cinnamates. When present, the preferred heat stabilizer is an organic phosphite, more specifically trisnonylphenyl phosphite as disclosed in U.S. Pat. No. 6,512,033, which is incorporated herein by reference. The heat stabilizer may comprise at least 0.01% by weight or at least 0.3% by weight, up to at most 5% by weight, up to 2% by weight or up to 1.0% by weight, based on the total weight of the adhesive composition. The adhesive composition may not include such a heat stabilizer.

[0147] As for UV light stabilizers, they include benzophenones and benzotriazoles.Specific UV light absorbers include those manufactured by BASF, such as TINUVIN P, TINUVIN 326, TINUVIN 213, TINUVIN 327, TINUVIN 571, TINUVIN 328, and those manufactured by Cytec, such as CYASORB UV-9, CYASORB UV-24, CYASORB UV-1164, CYASORB UV-2337, CYASORB UV-2908, CYASORB UV-5337, CYASORB UV-531 and CYASORB UV-3638.Among these, TINUVIN 571 is preferred. The one or more UV absorbers may comprise at least 0.1 wt%, at least 0.2 wt%, or at least 0.3 wt% of the adhesive composition weight, and may comprise up to 3 wt%, up to 2 wt%, or up to 1 wt%.

[0148] The adhesive composition of the present invention may further comprise one or more visible light stabilizers. Preferred visible light stabilizers include hindered amine visible light stabilizers such as TINUVIN® 144, TINUVIN® 622, TINUVIN® 77, TINUVIN® 123, TINUVIN® 765, CHIMASSORB® 944 available from Cytec; CYASORB® UV-500, CYASORB® UV-3581, CYASORB® UV-3346, all available from Ciba-Geigy. Of these, TINUVIN® 765 is a preferred choice. The visible light stabilizer may comprise at least 0.1%, at least 0.2%, or at least 0.3% by weight of the adhesive composition, and may comprise up to 3%, up to 2%, or up to 1.5% by weight of it.

[0149] Manufacturing method The adhesive composition of the present invention is prepared by mixing the ingredients of each component separately, preferably under inert and dry conditions and / or under vacuum, until a homogenous mixture is obtained. Once components A and B are mixed, they are stored in separate containers until use.

[0150] How to use In one aspect, the present invention provides a method for bonding a first substrate to a second substrate, the method comprising the steps of: (1) mixing component A and component B of the adhesive composition of the present invention to obtain a mixture; (2) applying the mixture to a first substrate, a second substrate, or both; (3) bringing the first substrate into adhesive contact with the second substrate; (4) Curing the mixture The present invention provides a bonding method comprising the steps of:

[0151] As noted above, a preferred method of providing the component adhesive of the present invention is in an airtight container, such as an airtight sealed tube, etc. The container is opened immediately prior to use.

[0152] The adhesive composition of the present invention may be applied by any application method, such as, for example, spreading, applying through a nozzle, either manually or with a robotic device.

[0153] In a preferred embodiment, one or both of the first and second substrates are selected from metal, glass, glass with primer, glass with enamel coating, plastic (e.g., polypropylene with talc or glass fiber), polycarbonate, sheet molding compound, composite material (e.g., carbon fiber reinforced epoxy, glass fiber reinforced polyamide). In a preferred embodiment, at least one of the first and second substrates is metal, particularly steel or aluminum, particularly preferably e-coated steel, e-coated aluminum. In a particularly preferred embodiment, both substrates are steel.

[0154] Curing begins as soon as components A and B are mixed. Typical curing conditions are 3-7 days at 23°C.

[0155] [Effects of the invention] The adhesive composition of the present invention has less than 0.1 wt. %, more preferably 0 wt. %, both monomeric contaminants and NCO content in the adhesive molecule, as measured according to ASTM D2572-97.

[0156] The adhesive compositions of the present invention containing CaO exhibit improved adhesive properties and retention of mechanical and adhesive properties after heat and weathering compared to those not containing CaO.

[0157] Adhesives of the invention containing CaO, after curing for 7 days at room temperature (RT), preferably exhibit an E modulus of 2 MPa or more, more preferably at least 2.5 MPa, when tested according to ISO 527-1.

[0158] The adhesive composition of the present invention containing CaO, after curing at RT for 7 days and heat treatment at 80° C. for 1 month, preferably exhibits an E modulus of 2 MPa or more, more preferably at least 2.5 MPa, when tested according to ISO 527-1.

[0159] The adhesive compositions of the invention containing CaO, after curing for 7 days at RT and weathering for 1 month as described in the examples, preferably exhibit an E modulus of 10 MPa or more, more preferably at least 12 MPa, when tested according to ISO 527-1.

[0160] Adhesives of the invention containing CaO, after curing for 7 days at room temperature (RT), preferably exhibit a tensile strength of 2.6 MPa or more, more preferably at least 2.7 MPa, when tested according to ISO 527-1.

[0161] The adhesive composition of the present invention containing CaO, after curing at RT for 7 days and heat treatment at 80°C for 1 month, preferably exhibits a tensile strength of 2.5 MPa or more, more preferably at least 2.7 MPa, when tested according to ISO 527-1.

[0162] The adhesive composition of the present invention containing CaO, after curing for 7 days at RT and weathering for 1 month, as described in the examples, preferably exhibits a tensile strength of 6 MPa or more, more preferably at least 6.5 MPa, when tested according to ISO 527-1.

[0163] The adhesive compositions of the present invention containing CaO and at least one phenolic antioxidant exhibit improved adhesive properties and retention of mechanical and adhesive properties after heat and weathering compared to those not containing CaO and at least one phenolic antioxidant.

[0164] The adhesives of the present invention containing CaO and at least one phenolic antioxidant, after curing for 7 days at room temperature (RT), preferably exhibit an E modulus of at least 2.3 MPa, more preferably at least 2.6 MPa, when tested according to ISO 527-1.

[0165] The adhesive composition of the present invention comprising CaO and at least one phenolic antioxidant, after curing at RT for 7 days and heat treatment at 80° C. for 1 month, preferably exhibits an E modulus of at least 3 MPa, more preferably at least 4 MPa, when tested according to ISO 527-1.

[0166] The adhesive composition according to the invention comprising CaO and at least one phenolic antioxidant, as described in the examples, after curing for 7 days at RT and weathering for 1 month, preferably exhibits an E modulus of at least 11 MPa, more preferably at least 13 MPa, when tested according to ISO 527-1.

[0167] The adhesives of the present invention containing CaO and at least one phenolic antioxidant, after curing for 7 days at room temperature (RT), preferably exhibit a tensile strength of at least 2.7 MPa, more preferably at least 2.8 MPa, when tested according to ISO 527-1.

[0168] The adhesive composition of the present invention comprising CaO and at least one phenolic antioxidant, after curing at RT for 7 days and heat treatment at 80° C. for 1 month, preferably exhibits a tensile strength of at least 2.7 MPa, more preferably at least 3 MPa, when tested according to ISO 527-1.

[0169] The adhesive composition according to the invention comprising CaO and at least one phenolic antioxidant, as described in the examples, after curing at RT for 7 days and weathering for 1 month, preferably exhibits a tensile strength of at least 6.5 MPa, more preferably at least 7 MPa, when tested according to ISO 527-1.

[0170] Using the lap shear adhesion test described in the Examples, adhesives of the invention containing CaO preferably have a lap shear strength of 2 MPa or greater, more preferably at least 2.3 MPa, after curing for 7 days at room temperature (RT), and exhibit a failure mode of 100% cohesive failure.

[0171] Using the lap shear adhesion test described in the Examples, adhesives of the invention containing CaO preferably have a lap shear strength of 2 MPa or greater, more preferably at least 2.5 MPa, after curing for one month at room temperature (RT), and exhibit a failure mode of 100% cohesive failure.

[0172] Particularly preferred embodiments The following are particularly preferred embodiments of the adhesive composition of the present invention. 1. (A) reacting at least one polyisocyanate with at least one polyol (resulting in intermediate I), and then reacting the resulting polyisocyanate with a polyol having formula I:

[0173] [ka]

[0174] (In the formula, R 1 and R 2 is independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl) a polyurethane prepolymer produced by reacting molecules of and optionally a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I. Includes wherein the molecule of formula I is used in an amount that will react with all of the NCO groups in intermediate I as well as any residual monomeric isocyanates. Component A; (B) Component B comprising a polyamine and, optionally, a catalyst capable of catalyzing the reaction of the amine with a moiety derived from a molecule of Formula I; A two-component polyurethane adhesive composition comprising: 1. An adhesive composition, wherein at least one of component A and component B comprises a catalyst capable of catalyzing a reaction between an amine and a moiety derived from a molecule of formula I, and component A has an NCO content of less than 0.1 weight percent as measured according to ASTM D2572-97. 2. (1) reacting at least one polyisocyanate with at least one polyol to produce intermediate I; (2) Formula I:

[0175] [ka]

[0176] (In the formula, R 1 and R 2 is independently selected from hydrogen and C1-C6 alkyl, n is an integer from 1 to 2, and R 3 is C1-C6 alkyl) reacting with a molecule of A method for producing a polyurethane prepolymer, comprising: A process for making wherein a molecule of formula I is used in an amount sufficient to react with all NCO groups of intermediate I and with residual monomeric polyisocyanates to result in an NCO content of less than 0.1 weight percent in component A as measured according to ASTM D2572-97. 3. Any one of embodiments 1-2, wherein the at least one polyol is selected from polyether polyols, polyester polyols (e.g., polycaprolactone), polybutadiene diols, polycarbonate diols, aliphatic diols (polyols), and mixtures of any of these. 4. Any one of embodiments 1-3, wherein the at least one polyol is a polyether polyol. 5. Any one of embodiments 1-4, wherein the at least one polyol is a diol, triol, or tetraol. 6. Any one of embodiments 1-5, wherein at least one polyol is a triol. 7. Any one of the preceding embodiments, wherein the at least one polyol is selected from polyoxyethylene, polyoxypropylene, polyoxybutylene, and polytetramethylene ether diols and triols, and mixtures thereof. 8. Any one of embodiments 1-7, wherein the at least one polyol is a polyoxypropylene ether triol. 9. Any one of embodiments 1-8, wherein the at least one polyol is a polyoxypropylene ether diol. 10. Any one of the preceding embodiments, wherein at least one polyol has a molecular weight of 1,500 to 3,000 Da. 11. Any one of the preceding embodiments, wherein the at least one polyol is a polyoxypropylene ether diol having a molecular weight of 1,500 to 3,000 Da. 12. Any of the preceding embodiments, wherein the at least one polyisocyanate is a diisocyanate or triisocyanate. 13. Any of embodiments 1-12, wherein the at least one polyisocyanate is selected from toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI), methylene bis(phenylisocyanate) (MDI, particularly 4,4'- and 4,2-MDI), and isophorone diisocyanate (IPDI). 14. Any of the preceding embodiments, wherein at least one polyisocyanate is HDI. 15. Any of the preceding embodiments, wherein the at least one polyisocyanate is used in an amount of 1.2 or more equivalents relative to the at least one polyol. 16. In the molecule of formula I, R 1 and R 2 Any one of the preceding embodiments, wherein is independently selected from H and C1-C4 alkyl. 17. In the molecule of formula I, R 1 and R 2 Any one of the preceding embodiments, wherein is independently selected from H and C1-C2 alkyl. 18. In the molecule of formula I, R 1 and R 2 Any one of embodiments 1-17, wherein is H. 19. Any one of embodiments 1-18, wherein in the molecule of formula I, n is 1. 20. In the molecule of formula I, R 3 Any one of embodiments 1-19, wherein is C1-C4 alkyl. 21. In the molecule of formula I, R 3 Any one of embodiments 1-20, wherein is C1-C2 alkyl. 22. In the molecule of formula I, R 3 Any one of embodiments 1-21, wherein is ethyl. 23. In the molecule of formula I, R 1 and R 2 is H, n is 1, and R 3 is ethyl [2-(ethoxycarbonyl)cyclopentanone, CPEE], any one of embodiments 1 to 22.

[0177] [ka]

[0178] 24. Any one of embodiments 1-23, wherein the molecule of formula I is used in an amount sufficient to react with all of the NCO groups of intermediate I. 25. Any of the preceding embodiments, wherein the molecule of Formula I is used in an amount sufficient to react with all of the NCO groups of intermediate I and any residual monomeric isocyanates. 26. Any of the preceding embodiments, wherein the at least one polyol and the at least one polyisocyanate are reacted in the presence of a catalyst comprising a zinc carboxylate. 27. Any one of embodiments 1-26, wherein intermediate I and a molecule of formula I are reacted in the presence of a catalyst comprising a zinc carboxylate. 28. Any of the preceding embodiments, wherein the at least one polyamine in component B is a diamine, a triamine, or a mixture thereof. 29. Any one of embodiments 1-28, wherein at least one polyamine is a triamine. 30. Any one of embodiments 1-29, wherein at least one polyamine has a molecular weight of at least 400 Da. 31. Any one of embodiments 1-30, wherein at least one polyamine has a molecular weight of at least 1,000 Da. 32. Any one of embodiments 1-31, wherein at least one polyamine has a molecular weight of at least 2,000 Da. 33. Any one of embodiments 1-32, wherein at least one polyamine has a molecular weight of 2,000 to 4,000 Da. 34. Any one of embodiments 1-33, wherein at least one polyamine has a molecular weight of 3,000 Da or about 3,000 Da. 35. Any one of embodiments 1-34, wherein at least one polyamine has primary amine groups. 36. Any of embodiments 1-35, wherein the at least one polyamine is selected from polyoxyalkylene polyamines having two or more amine groups per polyamine. 37. Any of embodiments 1-36, wherein the at least one polyamine is selected from polyoxyalkylene polyamines having three amine groups per polyamine. 38. Any of embodiments 1-37, wherein the at least one polyamine is selected from polyoxyalkylene polyamines having three amine groups per polyamine and a molecular weight of 2,000 to 4,000 Da. 39. Any one of embodiments 1-38, wherein the at least one polyamine is selected from polyamines having a propylene oxide polyether backbone. 40. At least one polyamine is General formula:

[0179] [ka]

[0180] of a trifunctional primary amine having an average molecular weight of approximately 440; Polypropylene oxide diamine having a molecular weight of about 400:

[0181] [ka]

[0182] ; The general formula:

[0183] [ka]

[0184] A difunctional, primary amine having an average molecular weight of about 2000. General formula:

[0185] [ka]

[0186] of approximately 3000 molecular weight triamine; General formula:

[0187] [ka]

[0188] of approximately 5,000 g / mol of triamine Any one of embodiments 1-39, selected from: 41. At least one polyamine has the general formula:

[0189] [ka]

[0190] Any one of the preceding embodiments, wherein the triamine is approximately 3.000 g / mol. 42. Any one of embodiments 1-41, wherein component A and / or component B comprises calcium oxide (CaO). 43. Any of the preceding embodiments, comprising CaO in component A and / or component B in an amount that results in a concentration in the mixture of components A and B of 2 to 6% by weight, based on the total weight of components A and B. 44. Any of the preceding embodiments, comprising CaO in component A and / or component B in an amount that results in a concentration in the mixture of components A and B of 3 to 5% by weight, based on the total weight of components A and B. 45. Any of the preceding embodiments, wherein component A and / or component B comprises at least one phenolic antioxidant. 46. ​​Any of the preceding embodiments, wherein Component A and / or Component B comprises at least one hindered phenolic antioxidant. 47. The component A and / or the component B is / are 4,6-bis(octylthiomethyl)-o-cresol (Irganox 1520L), pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (Irganox 1010), octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate] (Irganox 1076), N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) (Irganox 1098), 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4,6-triyl)tri-p-cresol (Irganox 1330), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Irganox 3114), ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (Irganox 245), benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester (Irganox 1135), 3,5-di-tert-butyl-4-hydroxycinnamic acid (Irganox 3125), hexamethylene bis(3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate) (Irganox 259), thiodiethylene bis[3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate] (Irganox 1035), and mixtures thereof. 48. Any one of embodiments 1 to 47, wherein component A and / or component B comprises at least one hindered phenolic antioxidant which is 4,6-bis(octylthiomethyl)-o-cresol (Irganox 1520L). 49. Any of the preceding embodiments, comprising at least one phenolic antioxidant in component A and / or component B in an amount that results in a concentration in the mixture of components A and B of 0.5 to 6% by weight, based on the total weight of components A and B. 50. Any of the preceding embodiments, comprising at least one phenolic antioxidant in component A and / or component B in an amount that results in a concentration in the mixture of components A and B of 1 to 3% by weight, based on the total weight of components A and B. 51. Any one of the preceding embodiments, wherein component A and / or component B comprises CaO and 4,6-bis(octylthiomethyl)-o-cresol (Irganox 1520L) in amounts that result in a concentration of CaO in the mixture of components A and B of 3 to 5 wt. % and a concentration of 4,6-bis(octylthiomethyl)-o-cresol (Irganox 1520L) in the mixture of components A and B of 1 to 3 wt. %, based on the total weight of components A and B. 52. Any one of the preceding embodiments, wherein component A and / or component B further comprises a plasticizer. 53. Any one of embodiments 1-52, wherein component A and / or component B further comprises a plasticizer that is diisononyl phthalate. 54. Any one of the preceding embodiments, wherein component A and / or component B further comprises an adhesion promoter. 55. Any one of the preceding embodiments, wherein component A and / or component B further comprises an adhesion promoter that is a silane. 56. Any one of the preceding embodiments, wherein component A and / or component B further comprises an adhesion promoter that is gamma-glycidoxypropyltrimethoxysilane. 57. Component A is a polyurethane prepolymer made from propylene oxide polyether diol with a molecular weight of 2,000 Da, 1,6-HDI and CPEE; ·Aluminum hydroxide; CaO and Any one of embodiments 1 to 56, including: 58. Component B is General formula:

[0191] [ka]

[0192] of approximately 3,000 g / mol of triamine; a catalyst capable of catalyzing the reaction of an amine with a moiety of formula I; Any one of embodiments 1 to 57, including: 59. Component B is General formula:

[0193] [ka]

[0194] of approximately 3,000 g / mol of triamine; a catalyst capable of catalyzing the reaction of an amine with a moiety of formula I; CaO and Any one of embodiments 1 to 58, including: 60. Any of the preceding embodiments, wherein the molecule of Formula I is used in an amount sufficient to react with all NCO groups of intermediate I and with residual monomeric polyisocyanate to provide an NCO content of less than 0.1 wt. % as measured according to ASTM D2572-97. 61. A method for bonding a first substrate to a second substrate, comprising the steps of: (1) mixing component A and component B of the adhesive composition according to any one of embodiments 1 to 60 to obtain a mixture; (2) applying the mixture to a first substrate, a second substrate, or both; (3) bringing the first substrate into adhesive contact with the second substrate; (4) Curing the mixture The bonding method comprising: 62. (1) a first substrate; (2) a second substrate; (3) An adhesive composition obtained by mixing component A and component B according to any one of embodiments 1 to 61. An adhesive assembly comprising: a first and a second substrate being in adhesive contact with the adhesive composition sandwiched therebetween; Glued assembly. EXAMPLES

[0195] [Table 1]

[0196] Preparation of Polyurethane Prepolymer for Component A Blocked polyurethane prepolymer 1 was prepared using the ingredients listed in Table 2.

[0197] [Table 2]

[0198] Voranol 2000L was added to a lab reactor and heated to 100°C (material temperature) under vacuum and stirring. After the material temperature reached 100°C, the material was cooled to 70°C under N2 and stirring. 1,6 Hexamethylene diisocyanate was added under stirring. After the material temperature reached 60°C, the catalyst was added. The bath temperature was set at 80°C. The mixture was cooled to 100°C (material temperature) under vacuum and stirring. 2 The reaction was allowed to proceed under N for 25 min. CPEE was added and the mixture was stirred and heated under N 2 The mixture was allowed to react under vacuum for 50 minutes. The NCO content was determined to be zero. The mixture was degassed under vacuum.

[0199] Adhesive compounding components A and B Adhesive formulation components A and B were prepared using the ingredients and amounts listed in Table 3.

[0200] [Table 3]

[0201] Component A was prepared by adding ingredients 1-3 to a laboratory mixer and mixing for 10 minutes at 120 rpm at RT. The mixture was removed from the mixer with a spatula. It was mixed for an additional 15 minutes at 120 rpm and RT under vacuum.

[0202] Component B was prepared by adding ingredients 1-7 to a laboratory mixer and mixing for 10 minutes at 120 rpm at RT. The mixture was removed from the mixer with a spatula. Component 8 was added and the mixture was mixed under vacuum at 120 rpm and RT for an additional 15 minutes.

[0203] mixture Bulk adhesive samples were dispensed from a double sided cartridge and applied by cartridge gun in a 1:1 ratio of component A to component B.

[0204] test viscosity Viscosity was measured on a Kinexus rheometer using a plate / cone setup with a 20 mm diameter cone at an angle of 4° and a gap of 0.144 mm. Measurements were performed at 23° C. Shear rate measurements were performed from 0.1 to 10 1 / s and Newtonian viscosity is reported.

[0205] Lap Shear Test Lap shear tests were carried out according to DIN EN 1465 using 1 mm thick e-coated (Cathoguard) steel substrates (DC04ZE50). The adhesive composition was applied and a second substrate was bonded. The adhesive overlap area was 25x10 mm and the adhesive thickness was 0.5 mm. The adhesive composition was cured at RT for 7 days before the lap shear tests. The tests were carried out on a Zwick tensiometer equipped with a 5 kN force measuring system, with a preload of 2 N and a towing speed of 10 mm / min. The tests were carried out at 23°C. The results are shown in Table 7 (immediately after curing) and Table 8 (after 1 month at 23°C).

[0206] Reference Example 1 exhibits lower lap shear strength immediately after curing than Examples 2 and 3 (Table 7), and also exhibits lower lap shear strength after storage at room temperature for one month (Table 8).

[0207] Tensile Test Tensile tests were performed according to ISO 527-1. Dogbones were cut from 2 mm thick plates cured at 23°C for at least 7 days. The preload was 1 N, the specimen width was 4 mm, and the pull rate was 200 mm / min. A 500 N force measuring system was used with a MuliXtens distance measuring system. The results are listed in Table 4 (immediately after curing), Table 5 (after 1 month at 80°C) and Table 6 (after 1 month of weather cycling).

[0208] The tensile strength of Reference Example 1 shows a significant decrease after storage at elevated temperature (80° C.), whereas Examples 2 and 3 essentially retain their tensile strength measured immediately after curing.

[0209] The tensile strength of Reference Example 1 dropped dramatically after one month of weather cycling, while Examples 2 and 3 actually increased in tensile strength.

[0210] Breaking Elongation The elongation at break was measured according to ISO 527-1. The results are shown in Table 7 (immediately after curing) and Table 8 (after 1 month at 23°C).

[0211] Weather Cycling Samples were subjected to the following 12 hour cycle: Heat to 80°C and 80% relative humidity (RH) for 60 minutes; 240 min at 80°C and 80% RH; Cool to -40°C for 120 minutes; 240 min at 40°C; Heat to 23°C for 60 minutes; Store at 80℃

[0212] molecular weight The molecular weight data of the polyurethane prepolymer was measured by gel permeation chromatography (GPC) using a Malvern Viscothek GPC max instrument, with tetrahydrofuran (THF) as the eluent, PL GEL MIXED D (Agilent, 300*7.5mm, 5μm) as the column, and MALVERN Viscotek TDA (integrated refractive index viscometer and light scattering) as the detector.

[0213] Pyrolysis under inert atmosphere Equipment: TA TGA 5500 Thermal degradation of the cured adhesives under inert atmosphere (N2) was measured using thermogravimetric analysis at 40-600°C for 30 minutes. Degradation was measured after 1 day of curing at RT, immediately after curing, after 1 month at 80°C, after 3 months at 80°C, after 1 month of weather cycling, and after 3 months of weather cycling. The results are listed in Table 9.

[0214] The lower the onset temperature of decomposition, the less stable the adhesive is. The results in Table 9 show that Reference Example 1 is significantly less stable after 1 and 3 months of storage at high temperature (80°C), especially after 1 and 3 months of weather cycling.

[0215] Thermal oxidative decomposition under O2 atmosphere Thermal degradation of the cured adhesives under O2 atmosphere was measured using thermogravimetric analysis at 40-600 °C for 30 min. Degradation was measured after 1 day of curing at RT, immediately after curing, after 1 month at 80 °C, after 3 months at 80 °C, after 1 month of weather cycling, and after 3 months of weather cycling. The results are listed in Table 10.

[0216] The lower the onset temperature of decomposition, the less stable the adhesive is. The results in Table 10 show that Reference Example 1 is significantly less stable after 1 and 3 months of storage at high temperature (80°C), especially after 1 and 3 months of weather cycling.

[0217] NCO content NCO measurements were performed according to ASTM D2572-97. This test method is applicable to isocyanate-containing fluids. These include monomers (e.g., methylene diphenyl diisocyanate MDI), prepolymers, and adhesive formulations. The isocyanate (NCO) samples were reacted with excess dibutylamine to form the corresponding urea. The NCO content was determined from the amount of dibutylamine consumed in the reaction. Results are reported as percent NCO (wt%).

[0218] Alternatively, infrared spectroscopy can be used to determine the -1 I searched for the NCO band in. Equipment: Agilent Technologies CARY 600 The adhesives of the present invention (Reference Example 1 and Examples 2 and 3) exhibited essentially 0 wt% NCO and 0 wt% free isocyanate in the polymer.

[0219] [Table 4]

[0220] [Table 5]

[0221] [Table 6]

[0222] [Table 7]

[0223] [Table 8]

[0224] [Table 9]

[0225]

Table 10

Claims

1. (A) reacting at least one polyisocyanate with at least one polyol (resulting in intermediate I), and then reacting the resulting mixture with a polyisocyanate having the formula I: 【Chemistry 1】 (In the formula, R 1 and R 2 are independently hydrogen and C 1 ~C 6 alkyl, n is an integer from 1 to 2, R 3 is C 1 ~C 6 a polyurethane prepolymer prepared by reacting a molecule of and optionally a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I; wherein the molecule of formula I is used in an amount to react with all NCO groups in intermediate I as well as residual monomeric isocyanates. (B) a polyamine, and optionally a component B comprising a catalyst capable of catalyzing the reaction of the amine with a moiety derived from a molecule of formula I, at least one of component A and component B comprises said catalyst capable of catalyzing said reaction between an amine and said moiety derived from said molecule of formula I, and component A has an NCO content of less than 0.1 weight percent as measured according to ASTM D2572-97.

2. 2. The adhesive composition of claim 1, wherein said at least one polyol is selected from polyether polyols, polyester polyols, polybutadiene diols, polycarbonate diols, aliphatic diols, and mixtures thereof.

3. The adhesive composition of claim 2 wherein said at least one polyol is a polyether polyol.

4. The adhesive composition of claim 1 , wherein the at least one polyol is a diol, triol, or tetraol.

5. The adhesive composition of claim 4 wherein said at least one polyol is a triol.

6. 2. The adhesive composition of claim 1, wherein said at least one polyol is selected from polyoxyethylene, polyoxypropylene, polyoxybutylene, and polytetramethylene ether diols and triols, and mixtures thereof.

7. The adhesive composition of claim 6 wherein said at least one polyol is a polyoxypropylene ether triol.

8. The adhesive composition of claim 6 wherein said at least one polyol is a polyoxypropylene ether diol.

9. The adhesive composition of claim 1 , wherein said at least one polyisocyanate is a diisocyanate or a triisocyanate.

10. 2. The adhesive composition of claim 1, wherein the at least one polyisocyanate is selected from toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI), methylene bis(phenylisocyanate) (MDI, in particular 4,4'- and 4,2-MDI) and isophorone diisocyanate (IPDI).

11. The adhesive composition of claim 10, wherein said at least one polyisocyanate is HDI.

12. 11. The adhesive composition of claim 10, wherein said at least one polyisocyanate is used in an amount of 1.2 or more equivalents relative to said at least one polyol.

13. In the molecule of formula I, R 1 and R 2 independently H and C 1 ~C 4 2. The adhesive composition of claim 1, wherein the alkyl group is selected from the group consisting of aryl, ... and alkyl.

14. 2. The adhesive composition of claim 1, wherein in said molecule of formula I, n is 1.

15. In the molecule of formula I, R 3 C 1 ~C 4 The adhesive composition of claim 1 , wherein the alkyl group is an alkyl group.

16. In the molecule of formula I, R 1 and R 2 is H, n is 1, R 3 is ethyl [2-(ethoxycarbonyl)cyclopentanone, CPEE], the adhesive composition of claim 1. 【Chemistry 2】

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