Hydrosilylation-curable polyether compound

Abstract

(a) a polyether having an average of 1.4 or more unsaturated carbon-carbon bonds per molecule, and (b) a combination of the following siloxane units that does not contain a phenyl group and that contain 90 mole percent or more of the following siloxane units: H(R 3 )2SiO 1 / 2 , SiO 4 / 2 , and optionally (R 3 )3SiO 1 / 2 (H(R 3 )2SiO 1 / 2 The average number of units per molecule is 2 or more, and SiO 4 / 2 The average number of units per molecule is 1 or more, (R 3 )3SiO 1 / 2 The average number of units per molecule is (R 3 )3SiO 1 / 2 Let the number of units be H(R 3 )2SiO 1 / 2 and (R 3 )3SiO 1 / 2 one or more silylhydride-functional polysiloxane crosslinkers, each of which contains a silylhydride functional group such that when divided by the sum of the units, the group is less than 0.7, 3 is independently selected at each occurrence from hydrocarbyl groups having 1 to 8 carbon atoms; and (c) a hydrosilylation catalyst, wherein the molar ratio of SiH / C=C in the composition is in the range of 0.3 to 10.

Description

[Technical field]

[0001] The present invention relates to addition reaction curable polyether compositions that do not require a phenyl-functionalized silicone crosslinker as a compatibilizing crosslinker.

[0002] Introduction Silane modified polymers (SMPs) are a class of materials consisting of an organic polymer backbone terminated with silane groups. SMPs are useful for formulating adhesives and sealants, such as room temperature vulcanizable (RTV) sealants, by exploiting the reactivity of the silane end groups for curing. Two types of SMPs currently available are silane terminated polyethers (STPEs) and silane modified polyurethanes (STPUs). Silane terminated polyethers tend to offer lower modulus and better durability than silane terminated polyurethanes, and are therefore often more desirable, especially in sealant applications.

[0003] SMP compositions cure by polycondensation and therefore require moisture to cure. Typically, polycondensation cure of SMP compositions utilizes atmospheric moisture for curing. This means that atmospheric moisture must be present to achieve cure. Furthermore, moisture must penetrate into the SMP composition in order for through cure to occur. As a result, the cure rate of an SMP composition depends on the available moisture and the rate at which it can penetrate the SMP material. Where atmospheric moisture is low (such as in dry regions), cure is difficult to achieve. Even when atmospheric moisture is present, moisture typically penetrates SMP materials slowly, so through cure can take hours to days to achieve anywhere. Moisture penetration is even more of a problem when SMP-based formulations are located in locations that require atmospheric moisture to travel long diffusion paths to reach the formulation. An additional problem with polycondensation curable SMP compositions is the generation of volatile organic compounds (VOCs), such as methanol, as they cure.

[0004] It is desirable to find alternatives to currently available SMP compositions that cure by mechanisms other than polycondensation to avoid the need for moisture and the generation of VOC by-products. In particular, it is desirable to identify addition-cured silane-modified polyether compositions that cure by mechanisms other than polycondensation. One alternative option is to cure using an addition-cured chemistry such as hydrosilylation. The challenge with hydrosilylation chemistry of polyether compositions is to achieve compatibility with the polyether and silicone crosslinker components, both of which are present in the composition, so that they are miscible. This challenge has been addressed in the prior art by incorporating phenyl groups into the silicone crosslinker to increase compatibility. However, phenyl-containing silicone materials are expensive due to their complexity of manufacture. It is therefore desirable to identify addition-cured polyether compositions that do not require phenyl-functionalized silicone crosslinkers, but have components that are compatible with each other and cure within 90 minutes at 80 degrees Celsius (°C), and preferably within 24 hours at 25°C. Summary of the Invention

[0005] The present invention provides addition curable polyether compositions having components that are compatible with each other, but do not require a phenyl-functionalized silicone crosslinker. The addition curable polyether compositions can be cured at 80 degrees Celsius (°C) in 90 minutes or less, and in some cases at 25°C in 24 hours or less. In fact, the entire composition may be free of a phenyl-functionalized silicone crosslinker, or even free of any phenyl-functionalized components at all.

[0006] The present invention relates to a method for producing a SiO 4 / 2 , H(R 1 )2SiO 1 / 2 and optionally (R 1 )3SiO 1 / 2 This is the result of the discovery that silylhydride functional silicone resins containing a combination of siloxane units that is 90 mole percent (mol %) or greater, and can be 95 mole % or greater, or even 99 mole % or greater, or even 100 mole %, based on all siloxane units in the resin (mol % being based on all siloxane units, preferably all copolymerized units, in the SiH functional polysiloxane), are compatible with alkenyl functional polyethers and suitable crosslinkers in phenyl-free silane modified polyether compositions that cure by addition chemistry rather than polycondensation.

[0007] In a first aspect, the present invention provides a polyether having (a) an average of 1.4 or more unsaturated carbon-carbon bonds per molecule, and (b) a polyether having no phenyl groups and having 90 mole percent or more of the following combination of siloxane units: H(R 3 )2SiO 1 / 2 , SiO 4 / 2 and optionally (R 3 )3SiO 1 / 2 (H(R 3 )2SiO 1 / 2 The average number of units per molecule is 2 or more, and SiO 4 / 2 The average number of units per molecule is 1 or more, (R 3 )3SiO 1 / 2 The average number of units per molecule is (R3 )3SiO 1 / 2 Let the number of units be H(R 3 )2SiO 1 / 2 and (R 3 )3SiO 1 / 2 a silylhydride-functional polysiloxane crosslinker having one or more combinations of silylhydride-functional polysiloxane crosslinkers, each of which is a number such that when divided by the sum of the units is less than 0.7, 3 is independently selected at each occurrence from hydrocarbyl groups having 1 to 8 carbon atoms; and (c) a hydrosilylation catalyst, wherein the molar ratio of SiH / C=C in the addition reaction curable polyether composition is in the range of 0.3 to 10.

[0008] In a second aspect, the invention is a process for using the addition reaction-curable polyether composition of the previous aspect, comprising disposing the addition reaction-curable polyether composition on another material and then curing the addition reaction-curable polyether composition by heating to 80° C. or greater.

[0009] The addition reaction curable polyether compositions of the present invention are useful, for example, as compositions that can be used as sealants or adhesives. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Test methods refer to the test method most recent as of the priority date of this document unless a date is given with the test method number. Reference to a test method includes both a reference to the testing society and the test method number. The following test method abbreviations and designations apply herein: ASTM refers to the American Society for Testing and Materials, EN refers to European Norm, DIN refers to the Deutsches Institut fur Normung, and ISO refers to the International Organization for Standards.

[0011] "Plurality" means two or more. "And / or" means "and, or in the alternative." All ranges are inclusive of the endpoints unless otherwise indicated.

[0012] Although the chemical structures herein show the propylene oxide units as [OCH2CH(CH3)], it should be understood and is intended that the chemical structures are not limited to that orientation of the propylene oxide. For example, the propylene oxide units can be [OCH2CH(CH3)], [OCH(CH3)CH2], or a combination of the two orientations.

[0013] The siloxane units can be characterized by the designations M, D, T, and Q. M represents the formula "(CH3)3SiO 1 / 2 " D refers to a siloxane unit having the formula "(CH3)2SiO 2 / 2 " T refers to a siloxane unit having the formula "(CH3)SiO 3 / 2 ". Q refers to a siloxane unit having the formula "SiO 4 / 2 " refers to siloxane units having the formula: " 1 / 2 ". Non-oxygen groups bonded to silicon atoms in M, D, and T units are methyl groups unless otherwise stated or indicated. Specifically, oxygen atoms having multiples of "1 / 2" subscripts indicate that the oxygen bridges the designated atom to a second atom, which is also designated with an oxygen having a multiple of "1 / 2" subscript. For example, ((CH3)3SiO 1 / 2 )(SiO 4 / 2 ) or MQ refers to an M unit bonded to a Q unit where an oxygen atom is shared between the silicon atom of the M unit and the silicon atom of the Q unit. The subscript 1 / 2 multiplier indicates how many oxygen atoms are in such a shared bonding arrangement with the silicon atom of the siloxane unit.

[0014] Reference to the designation of a siloxane unit with the suffix "type" refers to a siloxane unit in which any one or more than one methyl group is actually an R group (wherein R is a group other than methyl, such as hydroxyl, alkoxyl, or hydrocarbyl). Hydrocarbyls typically contain 1 to 8 carbon atoms. For example, R can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl.

[0015] A siloxane unit may include, as a superscript, a representation of a group bonded to the silicon atom in place of an alkyl group. For example, "M H The "M" type unit is an M type unit in which one R group is replaced with hydrogen: ((R 1 )2HSiO 1 / 2 ) refers to "M H " unit is an M unit in which one methyl is replaced by a hydrogen atom ((CH3)2HSiO 1 / 2 ) refers to T Ph The unit refers to a T unit in which a methyl group has been replaced with a phenyl group.

[0016] Chemical formula representations of polysiloxanes using the M, D, T, and Q abbreviations typically have subscripts associated with the unit identifiers that can refer to either the average molar ratio of that siloxane unit to all siloxane units in the molecule, or the average number of related siloxane units in the molecule. If the subscript associated with a siloxane unit is 1 or greater, the subscript refers to the average number of those siloxane units in the molecule. If the subscript associated with a siloxane unit is less than 1, the subscript refers to the average molar ratio of that siloxane unit to the number of moles of all siloxane units in the molecule. The absence of a subscript means that the value of the subscript is 1.

[0017] The addition reaction curable polyether composition of the present invention comprises a polyether having unsaturated carbon-carbon bonds, preferably in the form of allyl and / or methallyl functional groups. The polyether may be linear or branched, or a combination of linear and branched polyethers. The polyether may be free of phenyl groups. The polyether has an average of 1.4 or more unsaturated carbon-carbon bonds per molecule, preferably 1.6 or more, 1.7 or more, or even 1.8 or more, and may have an average of 2.0 or more unsaturated carbon-carbon bonds per molecule, but at the same time typically has an average of 5 or less, 4 or less, 3 or less, or even 2 or less unsaturated carbon-carbon bonds per molecule. Typically, the unsaturated carbon-carbon bonds are carbon-carbon double bonds (C=C).

[0018] The polyether is not particularly limited, and various polyethers can be used. A typical example is a polyether having a repeating (-R 1 -O-) units (wherein -R 1 The polyether may have one type of repeating unit or multiple types of repeating units. That is, R 1 may be the same or different. The polyether may be a linear or branched polymer. The polyether may, and typically does, contain small amounts of other units that may or may not repeat along the polymer chain. The other units may, for example, come from the initiator used to synthesize the polymer. The initiator may be any chemical species that can be catalyzed to polymerize the polyether precursor. Examples of suitable initiators include glycerol and 1,4-butanediol.

[0019] The main chain of the polyether is polyoxypropylene (i.e., the above-mentioned -R 1- is -CH2CH(CH3)-). In terms of commercial availability and processability, polyethers having polyoxypropylene as the main chain are preferred. It is preferred that all regions of the polyether other than the unsaturated carbon-carbon bond group have a polyoxyalkylene skeleton, but the regions may also contain other structural units. In such a case, the total amount of polyether skeletons in the polymer is preferably 80% by weight or more, more preferably 90% by weight or more, based on the weight of the polyether. The number average molecular weight of the polyether is preferably 3000 or more, even 5000 or more, but at the same time, is typically 50000 or less, preferably 40000 or less, from the viewpoint of processability and adhesive properties at room temperature. Polyethers having a number average molecular weight of less than 3000 often result in more brittle cured products, while polyethers having a number average molecular weight of more than 50000 result in more viscous and less processable products. The addition reaction curable polyether composition can include a combination of polyethers having different molecular weights, which may be desirable when a broad molecular weight distribution property is required or desired. The molecular weight is a number average molecular weight calculated in terms of polystyrene by gel permeation chromatography (GPC). The bond of the unsaturated carbon-carbon double bond group to the polyether is not particularly limited, and examples thereof include a direct bond of an alkenyl group ether, an ester bond, a carbonate bond, a urethane bond, and a urea bond.

[0020] The polyether can be, for example, a linear or branched allyl or methallyl protected polypropylene oxide or a combination thereof. Desirably, the polymer is selected from any one or any combination of more than one of the following three exemplary polyethers: First, a three-branched polypropylene oxide having the average chemical structure (I): (H2C=CHCH2-[OCH2CH(CH3)] m -O)3-R 2 (I) (In the formula, the value of m is the average number of propylene oxide units in a given polyether segment and may be the same or different for each of the three polyether segments, with the proviso that the value of m is greater than 0 in each of the three segments, and the average of the sum of all three values ​​of m is 60 or more, 80 or more, 100 or more, 125 or more, 150 or more, 200 or more, 250 or more, 300 or more, 350 or more, 375 or more, 385 or more, or even 400 or more, but at the same time is 1000 or less, 750 or less, 700 or less, 600 or less, 500 or less, 400 or less, or even 385 or less; R 2 is a trivalent hydrocarbyl group, i.e., a hydrocarbyl group having three polyether chains attached thereto. For example, R 2 may have the chemical structure -CH(CH2-)- with a polyether chain attached at each "-".

[0021] Second, diallyl end-capped polypropylene oxide having the average chemical structure (II): {CH2=CHCH2O-[CH2CH(CH3)O] n}2-R 4 (II) (In the formula, R 4 is preferably a divalent hydrocarbyl containing 1 or more carbon atoms, and may contain 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, or even 8 or more carbon atoms, while typically containing 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or even 3 or less carbon atoms; and the subscript n is R 4 R is the average number of propylene oxide units in each of the two polypropylene oxide groups extending away from each other, which may, independently at each occurrence, have an average value of 10 or more, 20 or more, 50 or more, 60 or more, 75 or more, 100 or more, or even 125 or more, but at the same time typically have an average value of 1600 or less, 1400 or less, 1200 or less, 1000 or less, 750 or less, 500 or less, 250 or less, or 200 or less, and may have an average value of 175 or less, 150 or less, 100 or less, 75 or less, 70 or less, or even 65 or less. One particularly desirable R 4The divalent hydrocarbyl is -CH(CH3)CH2-.

[0022] Third, di-methallyl end-capped polypropylene oxide having the average chemical structure (III): {CH2=C(CH3)CH2O-[CH2CH(CH3)O] o}2-R 4 (III) (In the formula, R 4 is preferably a divalent hydrocarbyl containing 1 or more carbon atoms, and may contain 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, or even 8 or more carbon atoms, while typically containing 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or even 3 or less carbon atoms; the subscript o represents R 4 R is the average number of propylene oxide units in each of the two polypropylene oxide groups extending away from each other, which may independently at each occurrence have an average value of 10 or more, 20 or more, 50 or more, 60 or more, 65 or more, 75 or more, 100 or more, or even 125 or more, but at the same time typically have an average value of 1600 or less, 1400 or less, 1200 or less, 1000 or less, 750 or less, 500 or less, 250 or less, 200 or less, and may have an average value of 175 or less, 150 or less, 100 or less, 75 or less, or even 70 or less. One particularly desirable R 4 A divalent hydrocarbyl is -CH(CH3)CH2-.

[0023] The addition reaction curable polyether composition also includes a combination of one or more silyl-hydride (SiH) functional polysiloxane crosslinkers. In particular, the SiH functional polysiloxane crosslinkers do not contain phenyl groups.

[0024] SiH functional polysiloxane crosslinkers are made up of a combination of siloxane units, i.e., SiO 4 / 2 , H(R 3 )2SiO 1 / 2 , and optionally (R 3 )3SiO 1 / 2The crosslinker preferably contains 90 mole percent (mol %) or more, and may contain 95 mole % or more, even 99 mole % or more, and even 100 mole %, where the mole % is based on the total siloxane units, preferably all copolymerized units, in the SiH-functional polysiloxane crosslinker. 3 is independently at each occurrence selected from hydrocarbyl groups having 1 or more carbon atoms, and may have 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, or even 7 or more, but typically at the same time, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or even 2 carbon atoms. 3 may be the same or may have different R 3 Preferably, each R 3 is a methyl group.

[0025] Generally, the SiH-functional polysiloxane crosslinker has an average of 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 10 or more, 15 or more, or even 20 or more SiO groups per molecule, but at the same time, typically 40 or less, 30 or less, 25 or less, 20 or less, or even 15 or less SiO groups. 4 / 2 It contains siloxane units.

[0026] Generally, SiH-functional polysiloxane crosslinkers are 3 )2SiO 1 / 2 Each molecule contains an average of 2 or more units, 3 or more, 4 or more, 5 or more, 6 or more, 10 or more, 15 or more, or even 20 or more units, but may also contain typically 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, 8 or less, 7 or less, 6 or less, or even 5 or less units.

[0027] Generally, the SiH-functional polysiloxane crosslinker is (R 3 )3SiO 1 / 2The unit may be 0 or more, 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 10 or more, or even 20 or more, but may also be typically 30 or less, 20 or less, 15 or less, 10 or less, 8 or less, 7 or less, 6 or less, or even 5 or less, with the proviso that (R 3 )3SiO 1 / 2 The average number of units per molecule is (R 3 )3SiO 1 / 2 Let the number of units be H(R 3 )2SiO 1 / 2 and (R 3 )3SiO 1 / 2 It may be a number such that when divided by the sum of the units is less than 0.7, and may be 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, or even zero.

[0028] Siloxane "resins" contain T-type and Q-type siloxane units, typically non-fully condensed Q-type, T-type, and sometimes D-type siloxane units with "-OZ" groups, where Z is selected from H or an alkyl group having 1 or more or more than 1, but at the same time 8 or less, typically 6 or less, carbon atoms. Generally, the concentration of -OZ groups in a siloxane resin is 5 mole percent (mol%) or less, based on the number of moles of siloxane units in the resin. As used herein, a "resin" is presumed to contain up to 5 mole% based on the number of moles of siloxane units in the resin, even if the -OZ component is not specified in the resin formula.

[0029] The relative concentrations of the allyl- and / or methallyl-functional polyether and the SiH-functional polysiloxane crosslinker are such that the molar ratio of SiH / C=C bonds in the addition reaction curable polyether composition is 0.3 or more, preferably 0.4 or more, and can be 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1 or more, or even 1.5 or more, but at the same time desirably is 10 or less, preferably 9 or less, 8 or less, 7 or less, 6 or less, even 5 or less, 4 or less, or even 3 or less.

[0030] The addition reaction curing polyether composition further comprises a hydrosilylation catalyst.Typically, the hydrosilylation catalyst is a platinum-based hydrosilylation catalyst.The platinum-based hydrosilylation catalyst includes compounds and complexes such as platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstet's catalyst), platinum-carbonyl complexes, platinum cyclovinylmethylsiloxane complexes, platinum acetylacetonate (acac), cyclopentedienyl alkyl platinum, platinum black, platinum compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid and monohydric alcohol, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum dichloride, and complexes of platinum compounds with olefins or low molecular weight organopolysiloxanes, or platinum compounds microencapsulated in matrix or core-shell structure. The catalyst may be a supported Pt catalyst, in which Pt metal particles or compounds are adsorbed or absorbed onto a support material such as carbon or alumina. The hydrosilylation catalyst may be part of a solution containing complexes of platinum with low molecular weight organopolysiloxanes, including 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes with platinum. These complexes may be microencapsulated in a resin matrix. Other transition or noble metal compounds, such as di-μ.-carbonyldi.-π.-cyclopentadienyldinickel, may also be used as hydrosilylation catalysts.

[0031] The addition reaction curing type polyether composition contains an average of two SiH groups per molecule, and is SiO 4 / 2 The chain extender may or may not further comprise a chain extender component that does not comprise siloxane units. The chain extender may or may not comprise a phenyl group. In one example, the chain extender has the average chemical composition: HR 3 2SiOPh2SiOSiR 3 2H (wherein "Ph" refers to a phenyl group and R 3is as defined above, and is preferably methyl. The concentration of the chain extender is typically 2 wt% or less, and can be 1.8 wt% or less, 1.6 wt% or less, 1.4 wt% or less, 1.2 wt% or less, 1.0 wt% or less, 0.8 wt% or less, 0.6 wt% or less, 0.3 wt% or less, 0.1 wt% or less, or even 0 wt% of the weight of the addition curable polyether.

[0032] The addition reaction curable polyether composition may or may not further comprise a hydrosilylation catalyst inhibitor. Examples of suitable hydrosilylation catalyst inhibitors include any one or any combination of more than one of the following compounds: 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, 3-phenyl-1-butyn-3-ol, 1-ethynyl-1-cyclohexanol, 1,1-dimethyl-2-propynyl)oxy)trimethylsilane, and methyl(tris(1,1-dimethyl-2-propynyloxy)). acetylene-based compounds such as silanes; ene-yne ​​compounds such as 3-methyl-3-penten-1-yne, and 3,5-dimethyl-3-hexen-1-yne; triazoles such as benzotriazole; hydrazine-based compounds; phosphine-based compounds; mercaptan-based compounds; cycloalkenylsiloxanes including methylvinylcyclosiloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane.

[0033] The concentration of the hydrosilylation catalyst inhibitor as a molar ratio to platinum from the catalyst can be 0 or more, 0.5 or more, 1.0 or more, 5.0 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, or even 100 or more, but at the same time is typically 200 or less, 100 or less, 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, or even 1.0 or less.

[0034] The addition reaction curable polyether composition may or may not further comprise an "additional" SiH functional crosslinker containing an average of 2 or more, preferably 3 or more, SiH functional groups per molecule, which does not meet the above qualifications for a SiH functional polysiloxane crosslinker. The additional SiH functional crosslinker may or may not contain a Ph group. Furthermore, the SiH functional crosslinker may be a SiO 4 / 2 It may contain siloxane units or SiO 4 / 2 It may not contain siloxane units.

[0035] The addition reaction curable polyether composition may be free of SiH functional polysiloxanes having phenyl functionality. The SiH functional crosslinker may be cyclic or acyclic. The additional SiH functional crosslinker may also be acyclic. The addition reaction curable polyether composition may be free of cyclic SiH functional crosslinkers.

[0036] The invention further includes a process for using the addition reaction curable polyether composition, which comprises disposing the addition reaction curable polyether composition on another material, such as a substrate, and then curing the addition reaction curable polyether composition, preferably by heating to a temperature of 80 degrees Celsius (°C) or greater. EXAMPLES

[0037] Table 1 identifies the components used in the following examples, where Me refers to methyl and Ph refers to phenyl.

[0038] [Table 1] DOWSIL is a trademark of The Dow Chemical Company. SYL-OFF is a trademark of Dow Corning Corporation.

[0039] Preparation of sample compositions The components of the sample compositions are shown in the table below. The polyether component is dried under vacuum at 110 degrees Celsius (°C) for 12 hours and stored in a glove box. The polyether is combined with the catalyst component in the glove box using a Flacktec SpeedMixer™ (Flacktek SpeedMixer is a trademark of Flacktec, Inc.) at 2500 revolutions per minute (RPM) for 30 seconds. While in the glove box, the SiH crosslinker component is added and mixed with the Flacktek SpeedMixer™ at 2500 RPM for 30 seconds.

[0040] The samples are cured in an open cup at 80° C. for 30 or 90 minutes as indicated in the table below.

[0041] Characterization of sample composition Compatibility. Compatibility of the components of the composition is assessed by visual inspection of the composition mixture in the glass vial. A "clear" or "T" mixture indicates complete compatibility. A "cloudy" or "H" mixture indicates particulate compatibility. An "opaque" or "O" mixture indicates immiscible and incompatible.

[0042] Cure Results. To determine the state of cure, cure ratings are performed on each composition after curing at 80°C for 30 and 90 minutes. A value of "1" is assigned to a sample that is "fully cured" into a solid piece of material that has a solidified surface that is evident from poking the surface with a spatula and is visually uniform from top to bottom. A value of "2" is assigned to a sample that is "cured but sticky", a cured composition that has a sticky surface. A value of "3" is assigned to a sample that increases in viscosity but has not cured into a solid piece of material. A value of "4" is assigned to a sample that remains fluid (remail) without a significant change in viscosity and is considered an "uncured" sample.

[0043] Samples and Results Tables 2 and 3 below list the components of each sample in grams (parts by weight of hydrosilylation catalyst per million parts by weight of composition), as well as the compatibility and cure evaluation results.

[0044] The only compositions in Table 2 that achieve compatibility and full cure even in 80 minutes are those containing only SiH-functional crosslinkers with phenyl functionality.

[0045] Each of the compositions in Table 3 exhibits compatible components and full cure within 80 minutes, with some reaching full cure in as little as 30 minutes. Each of the compositions in Table 3 does not contain phenyl functionality and contains 90 mole percent or more of the following combination of siloxane units: H(R 3 )2SiO 1 / 2 , SiO 4 / 2 , and optionally (R 3 )3SiO 1 / 2 (H(R 3 )2SiO 1 / 2 The average number of units per molecule is 2 or more, and SiO 4 / 2 The average number of units per molecule is 1 or more, (R 3 )3SiO 1 / 2 The average number of units per molecule is (R 3 )3SiO 1 / 2 Let the number of units be H(R 3 )2SiO 1 / 2 and (R 3 )3SiO 1 / 2 A SiH-functional crosslinker is used, which contains a number such that when divided by the sum of the units, it is less than 0.7, where R 3 is independently selected at each occurrence from a hydrocarbyl group having 1 to 8 carbon atoms. In particular, Table 3 includes compatible compositions including combinations of such crosslinkers along with crosslinkers from Table 2 that did not achieve compatibility and / or cure but do achieve compatibility and / or cure when blended with a crosslinker from Table 3.

[0046] [Table 2]

[0047] [Table 3]

Claims

1. An addition reaction curable polyether composition, a. a polyether having an average of 1.4 or more unsaturated carbon-carbon bonds per molecule; b. A siloxane having no phenyl groups and having 90 mole percent or more of the following combination of siloxane units: H(R ３ ) ２ SiO １／２ , SiO ４／２ , and optionally (R ３ ) ３ SiO １／２ (H(R ３ ) ２ SiO １／２ The average number of units per molecule is 2 or more, and SiO ４／２ The average number of units per molecule is 1 or more, and (R ３ ) ３ SiO １／２ The average number of units per molecule is (R ３ ) ３ SiO １／２ The number of units is H(R ３ ) ２ SiO １／２ and (R ３ ) ３ SiO １／２ a silylhydride-functional polysiloxane crosslinker (wherein R ３ is independently selected in each occurrence from hydrocarbyl groups having 1 to 8 carbon atoms; c. a hydrosilylation catalyst; Including, an SiH / C═C molar ratio in the addition reaction curable polyether composition in the range of 0.3 to 10;

2. Contains an average of two silylhydride groups per molecule and SiO ４／２ 10. The addition reaction curable polyether composition of claim 1, further comprising a chain extender component that does not contain siloxane units.

3. 10. The addition reaction curable polyether composition of claim 1, wherein the addition reaction curable polyether composition further comprises a hydrosilylation catalyst inhibitor.

4. 2. The addition reaction curable polyether composition according to claim 1, wherein the molar ratio of SiH / C═C in the addition reaction curable polyether composition is in the range of 0.4 to 5.

5. 2. The addition reaction curable polyether composition according to claim 1, wherein the unsaturated carbon-carbon bond of the polyether is part of an allyl group or a methallyl group.

6. 2. The addition reaction curable polyether composition of claim 1, wherein the polyether is any one or any combination of more than one of the following polyethers: (i) A tri-branched polypropylene oxide having the average chemical structure (I): (H ２ C=CHCH ２ -[OCH ２ CH (CH ３ )] ｍ -O) ３ -R ２ (I) (The value of m is the average number of propylene oxide units in a given polyether segment and may be the same or different for each of the three polyether segments, provided that the value of m is greater than 0 in each of the three segments, the average sum of all three values ​​of m is greater than or equal to 60 and less than or equal to 1000, and R ２ is a trivalent hydrocarbyl group (ii) Diallyl end-capped polypropylene oxide having the average chemical structure (II): {CH ２ =CHCH ２ O-[CH ２ CH (CH ３ )O] ｎ } ２ -R ４ (-I) (In the formula, R ４ is a divalent hydrocarbyl and the subscript n is R ４ and (iii) Dimethallyl end-capped polypropylene oxide having the average chemical structure (III): {CH ２ =C(CH ３ )CH ２ O-[CH ２ CH(CH ３ )O] ｏ } ２ -R ４ (III) (In the formula, R ４ is a divalent hydrocarbyl and the subscript o is R ４ and independently in each occurrence having an average value of 10 or greater while having an average value of 1600 or less).

7. 10. The addition-curable polyether composition of claim 1, wherein the addition-curable polyether composition further comprises an additional silyl hydride-functional crosslinker.

8. 10. The addition-curable polyether composition of claim 1, wherein the addition-curable polyether composition does not include a silyl-hydride functional polysiloxane that also has phenyl functionality.

9. The silylhydride functional crosslinker has an average of 5-6 SiO groups per molecule. ４／２ unit, 4 to 10 H(R ３ ) ２ SiO １／２ , and 0 to 5 (R ３ ) ３ SiO １／２ Each R ３ 2. The addition reaction curable polyether composition of claim 1, wherein each occurrence is independently selected from hydrocarbyl groups having 1 to 8 carbon atoms.

10. 10. A process for using the addition reaction-curable polyether composition of any one of claims 1 to 9, comprising disposing the addition reaction-curable polyether composition on another material and then curing the addition reaction-curable polyether composition by heating to 80°C or above.