Anhydrides and Aromatically Functionalized Polyorganosiloxanes

Abstract

The polyorganosiloxane has anhydride functionality and aromatic functionality, the carbon of the aromatic functionality being separated from the carbon of the carbonyl group of the anhydride functionality by a carbon chain, and the polyorganosiloxane contains 5% or more by weight of silicon atoms based on the weight of the polyorganosiloxane.

Description

Technical Field

[0001] The present invention relates to an anhydride-functional polysiloxane, a method for producing an anhydride-functional polysiloxane, and a composition containing an anhydride-functional polysiloxane.

Background Art

[0002] Introduction Anhydride-functional polysiloxanes are useful, for example, in high-value personal care applications for introducing hydrophilicity into silicone products. The anhydride functional group also provides a reactive functional group to the polyorganosiloxane by its ability to hydrolyze to form carboxylic acid groups or to react directly with amines or other functional groups in crosslinking reactions to form elastomers. The anhydride group can be further functionalized by various additional reactions such as esterification and amination. The anhydride group provides synthetic versatility in its ability to undergo condensation reactions with a wide range of polymers such as polyesters, polyamides, urethanes, and acrylates. Compounds such as polyorganosiloxanes containing anhydride groups are widely useful as intermediates due to their versatility in coupling reactions with other organic compounds.

[0003] The hydrophilic properties of anhydride-functional polyorganosiloxanes can also pose problems. For example, anhydride-functional polyorganosiloxanes tend to lack compatibility with organic compounds with which it is desirable to blend and react, such as styrene-based, epoxy, polycarbonate, polyester, polyamide, polyimide, urethane and acrylic organic compounds. As a result, it can be difficult to mix the polyorganosiloxane with these types of organic compounds to form a homogeneous reaction mixture.

[0004] It is desirable to specify an anhydride-functional polyorganosiloxane that also contains a functional group that makes the compound more compatible with organic compounds such as styrene-based, epoxy, polycarbonate, polyester, polyamide, polyimide, urethane, and acrylic. It is particularly desirable to specify an anhydride-functional polyorganosiloxane having an aromatic functional group, as well as a method for preparing such a polyorganosiloxane. Even more desirable is to specify an anhydride-functional polyorganosiloxane having an aromatic functional group separated from the carbon of the carbonyl (-C=O) group of the anhydride functional group by a carbon chain, preferably a carbon chain having three or fewer non-aromatic carbon atoms, preferably two or more non-aromatic carbon atoms.

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention provides an anhydride-functional polyorganosiloxane that also contains a functional group that makes the compound more compatible with organic compounds such as styrene-based, epoxy, polycarbonate, polyester, polyamide, polyimide, urethane, and acrylic. The present invention provides an anhydride-functional polyorganosiloxane having an aromatic functional group, as well as a method for preparing such a polyorganosiloxane. The present invention provides an anhydride-functional polyorganosiloxane having an aromatic functional group separated from the carbonyl carbon of the anhydride functional group by a carbon chain, and further a carbon chain having three or fewer non-aromatic carbon atoms and simultaneously two or more non-aromatic carbon atoms.

[0006] The present invention is the result of discovering a free radical reaction for combining an alkenyl-functional polyorganosiloxane with an anhydride functional group by incorporating an aromatic functional group into a polyorganosiloxane and incorporating an aromatic group within three carbon-carbon single bonds from the carbonyl group of the anhydride functional group, when carried out in the presence of an aromatic compound having an alpha hydrogen atom and / or an aromatic free radical initiator and / or an aromatic photoinitiator. Surprisingly, in the same reaction for incorporating an anhydride functional group, the free radical reaction can be a one-pot reaction in which all components are included together during the reaction. **Means for Solving the Problems**

[0007] In a first aspect, the present invention is a polyorganosiloxane having an anhydride functional group and an aromatic functional group, wherein the carbon of the aromatic functional group is separated from the carbon of the carbonyl group of the anhydride by a carbon chain (preferably a carbon chain of three or fewer, or two or fewer non-aromatic carbon atoms, simultaneously having one or more, preferably two or more non-aromatic carbon atoms), and the polyorganosiloxane contains 5% by weight or more of silicon atoms based on the weight of the polyorganosiloxane.

[0008] In a second aspect, the present invention is a process for producing the polyorganosiloxane of the first aspect, the process comprising (a) combining (i) an unsaturated organosiloxane, (ii) an unsaturated anhydride compound, (iii) a free radical initiator or a photoinitiator, and (iv) a solvent, and (b) initiating a free radical reaction by triggering the free radical initiator or the photoinitiator, wherein the solvent is an aromatic compound having an alpha hydrogen atom and / or the free radical initiator and / or the photoinitiator is aromatic.

[0009] In a third aspect, the present invention is a curable composition comprising (a) the polyorganosiloxane of the first aspect, and (b) an organopolysiloxane containing on average at least two silicon-bonded amines or two silicon-bonded epoxy groups per molecule.

[0010] The polyorganosiloxane of the present invention is useful, for example, in preparing the curable composition of the present invention.

Embodiments for Carrying Out the Invention

[0011] The test method refers to the latest test method at the priority date of this document when the test method is not dated with a test method number. The reference to the test method includes both the reference of the test society and the test method number. In this specification, the following abbreviations and identifiers of test methods are applicable, where ASTM refers to the American Society for Testing and Materials, EN refers to the European Electrical Standard, DIN refers to the German Industrial Standard, and ISO refers to the International Organization for Standardization.

[0012] A material specified only by a product name or trade name refers to a material sold under that product name or trade name at the priority filing date of this document, unless otherwise stated in this specification.

[0013] "Plurality" means two or more. "And / or" means "and, or alternatively". Unless otherwise specified, the entire range includes the endpoints.

[0014] "C x-y " type of designation means having x or more and y or less carbon atoms.

[0015] "Non-aromatic" carbon is a carbon atom that is not part of an aromatic ring. "Aromatic" carbon is a carbon atom that is part of an aromatic ring. "Non-aromatic" carbon bond is a bond between non-aromatic carbons.

[0016] Polysiloxane is composed of a plurality of siloxane units. Polyorganosiloxane contains a plurality of siloxane units, and one or more siloxane units contain organic functional groups. Siloxane units are generally characterized by the names M, D, T, and Q. M generally refers to a siloxane unit having the formula "R3SiO 1 / 2 ". D generally refers to a siloxane unit having the formula "R2SiO 2 / 2refers to a siloxane unit having 」. T generally refers to a siloxane unit having the formula 「RSiO 3 / 2 」. Q refers to a siloxane unit having the formula 「SiO 4 / 2 」. R is usually, each independently, selected from the group consisting of hydrogen, hydroxyl, alkoxy, or alkyl (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl), substituted alkyl such as trifluoropropyl and nonafluorohexyl, alkenyl (such as vinyl, allyl, and hexenyl), phenyl and substituted phenyl, any carbon-bonded substituent, and the 「OZ」 group (wherein O corresponds to oxygen and Z corresponds to a component selected from the group consisting of metal cations, alkyl, substituted alkyl, and hydrogen). 「Polyorganosiloxane」 is a polysiloxane in which at least one R group is an organic moiety. In particular, an oxygen atom having a subscript that is a multiple of 「1 / 2」 indicates that the oxygen bridges a particular atom to a second atom, and the second atom is also specified by an oxygen having a subscript that is a multiple of 「1 / 2」. For example, 「(SiO 4 / 2 )(HO 1 / 2 )」 refers to a Q-type group having a silicon atom bonded to hydrogen via a single oxygen.

[0017] 「Pendant」 means extending therefrom. Thus, a group pendant from a silicon atom of a polysiloxane is a group extending from any silicon atom in the polysiloxane. 「Terminal pendant」 extending from a silicon atom of a polysiloxane is a group extending from a silicon atom of an M siloxane unit.

[0018] The polyorganosiloxane of the present invention is not limited, in its broadest sense, with respect to the siloxane units it contains. In this regard, the polyorganosiloxane can contain any combination of one or more siloxane units selected from the group consisting of M, D, T, and Q siloxane units. For example, the polyorganosiloxane can contain M and D units and can be free of siloxane units other than M and D units. As an alternative, the polyorganosiloxane can contain M and Q units and can be free of siloxane units other than M and Q units. As yet another alternative, the polyorganosiloxane can contain M, D, and T units and can be free of siloxane units other than M, D, and T. The polyorganosiloxane of the present invention contains, based on the weight of the polyorganosiloxane, 5 weight percent (wt%) or more, preferably 7.5 wt% or more, of silicon atoms and can contain 10 wt% or more of silicon atoms. When the structure of the polyorganosiloxane is known, the weight percent of silicon in the polyorganosiloxane is determined from the molecular weights of the atoms constituting the polyorganosiloxane. When the structure of the polyorganosiloxane is not known, the weight percent of silicon can be determined using the following formula. % Silicon by weight = 100 * (n si * 28.09) / Σ i Z (n i * M i )。

[0019] In the formula, n si is the number of silicon atoms in the average structure of the organopolysiloxane determined by nuclear magnetic resonance spectroscopy techniques, gel permeation chromatography techniques, and / or gas chromatography / mass spectrometry techniques, the constant 28.09 is the atomic weight of silicon (in dalton units), n i and M iis the number of atoms of species i and the atomic weight (in daltons) of species i present in the average structure of the organopolysiloxane. The total range includes the total number of unique species present in the average structure of the organopolysiloxane such that the sum equals the total formula weight of the average structure of the organopolysiloxane.

[0020] Preferably, the pendant groups extending from the silicon atoms that do not contain both an anhydride functional group and an aromatic functional group contain 8 or fewer carbons and can contain 7 or fewer, and more preferably 6 or fewer carbons.

[0021] The polyorganosiloxane of the present invention has both an anhydride functional group and an aromatic functional group.

[0022] The anhydride functional group has the following structure: -C(=O)-O-C(=O)-. The anhydride functional group can be a cyclic anhydride (e.g., maleic anhydride) that is part of a ring of atoms to which a single-bonded oxygen and a carbonyl carbon are attached, and is preferably a cyclic anhydride. One desirable polyorganosiloxane of the present invention contains maleic anhydride residues (i.e., the components of the maleic anhydride molecule remaining after reacting the carbon-carbon double bond in vinyl polymerization).

Chemical formula

[0023] An aromatic functional group is a hydrocarbon or substituted hydrocarbon having a cyclic structure of bonded carbons with pi electrons delocalized around the carbons of the cyclic structure (aromatic ring). In this specification, the aromatic functional group and the aromatic ring are interchangeable. A phenyl group is an example of an aromatic functional group. The aromatic functional group may be substituted, may be bonded to a carbon atom forming an aromatic ring, and means a moiety that can be pendant from a carbon atom. For example, a tolyl group and a benzyl group are examples of substituted aromatic functional groups having a methyl or methylene group bonded to a carbon atom forming an aromatic ring and pendant from the carbon atom. Desirably, the aromatic functional group is monocyclic, which means that there is only one aromatic ring forming the aromatic functional group (in contrast to, for example, a naphthalene group containing two aromatic rings).

[0024] The carbon of the aromatic functional group is separated from the carbon of the carbonyl group of the anhydride functional group by a non-aromatic carbon chain. This means that the carbon of the carbonyl group of the anhydride functional group is bonded to a carbon that is directly or indirectly bonded to a carbon atom of the aromatic ring of the aromatic functional group via another non-aromatic carbon bond. For example, the residue of maleic anhydride can be bonded to the methylene carbon of a benzyl group to form a moiety having a carbonyl carbon of the anhydride functional group separated from the carbon of the aromatic functional group by two carbons. Desirably, the carbon chain is one or more non-aromatic carbons, can be two or more non-aromatic carbons, but at the same time, desirably, is six or fewer non-aromatic carbons, five or fewer non-aromatic carbons, four or fewer non-aromatic carbons, three or fewer non-aromatic carbons, or even two or fewer non-aromatic carbons. Determine the number of non-aromatic carbons that separate the aromatic carbon in the aromatic functional group from the carbonyl carbon of the anhydride functional group, preferably from the reaction expected from the reactants forming the polyorganosiloxane. Further, or alternatively, 13 C and 1 Determine the number of carbons that separate the aromatic functional group from the carbonyl carbon of the anhydride functional group by 13C and 1H nuclear magnetic resonance (NMR) analysis.

[0025] Typically, the anhydride functional group and the aromatic functional group are on the same pendant group extending from a single silicon atom of the polyorganosiloxane. Generally, when the anhydride functional group and the aromatic functional group are on the same pendant group extending from a single silicon atom of the polyorganosiloxane, the aromatic functional group is further away from the silicon atom along the pendant moiety than the anhydride functional group. Further, the anhydride functional group can be separated from the silicon atom to which it is bonded by a carbon chain, preferably a hydrocarbon chain. Typically, the carbon chain separating the silicon atom of the anhydride functional group from the nearest carbonyl carbon has a length of two or more carbons, preferably three or more carbons, while at the same time, it is usually eight or fewer carbons, seven or fewer carbons, six or fewer carbons, five or fewer carbons, four or fewer carbons, or three or fewer carbons.

[0026] The polyorganosiloxane of the present invention is the result of discovering a specific reaction process for making polyorganosiloxanes having both anhydride and aromatic functional groups. This process involves (a) forming a reactive composition by combining (i) an unsaturated polyorganosiloxane, (ii) an unsaturated anhydride compound, (iii) a free radical initiator and / or a photoinitiator, and (iv) a solvent, and (b) initiating a free radical reaction by triggering the free radical initiator and / or the photoinitiator. Surprisingly, it has been discovered that such a process results in a free radical reaction that incorporates both the anhydride compound and the aromatic component into the polyorganosiloxane. When the initiator is aromatic, it can bond onto the polyorganosiloxane when the free radical reaction is initiated. Generally, since the reaction is carried out at a relatively low initiator concentration, it is desirable to carry out the reaction in an aromatic solvent having an alpha hydrogen in order to provide a higher concentration of aromatic molecules that can be incorporated into the polyorganosiloxane. It is believed that removal of the alpha hydrogen of the solvent generates radicals that allow the solvent molecules to participate in (and even initiate) free radical reactions with unsaturated groups on other components.

[0027] An unsaturated polyorganosiloxane is typically a polyorganosiloxane containing, on average, one or more pendant unsaturated groups per molecule bonded to silicon atoms. The pendant unsaturated groups usually contain up to six carbons (e.g., hexenyl), up to five carbons, up to four carbons, up to three carbons (e.g., allyl), and can contain up to two carbons (vinyl group). Desirably, the pendant unsaturated group is a terminal unsaturated alkenyl group, which means that at the end of the carbon chain away from where a hydrogen atom would have been removed to form the alkenyl group from the corresponding alkene group, there is a carbon-carbon double bond between the terminal carbon and the adjacent carbon. For example, an allyl group is a terminal unsaturated alkenyl group. To avoid misunderstanding, a vinyl group is also considered a terminal unsaturated alkenyl group. Desirably, the pendant unsaturated group is selected from the group consisting of vinyl, allyl, and hexenyl groups, more preferably vinyl and allyl groups, and most preferably vinyl.

[0028] The unsaturated polyorganosiloxane is not limited, in its broadest sense, with respect to the siloxane units it contains. In this regard, the polyorganosiloxane can contain any combination of one or more siloxane units selected from the group consisting of M, D, T, and Q siloxane units. The unsaturated polyorganosiloxane contains 5 wt% or more, preferably 7.5 wt% or more, more preferably 10 wt% or more silicon atoms, based on the weight of the polyorganosiloxane. Determine the weight % of silicon in the polyorganosiloxane as described above. Preferably, the pendant groups extending from the silicon atoms contain up to eight carbons and can contain up to seven, and even up to six carbons. The polyorganosiloxane may or may not contain silanol groups and typically has a concentration of 5 wt% or less, preferably 4 wt% or less, 3 wt% or less, 2 wt% or less, and even 1 wt% or less, based on the weight of the polyorganosiloxane. 29 Determine the concentration of silanol groups by Si NMR.

[0029] Examples of suitable unsaturated polyorganosiloxanes include ViMe2SiO 1 / 2 (Me2SiO 1 / 2 ) a O 1 / 2 SiMe2Vi, ViMe2SiO 1 / 2 (MeViSiO 1 / 2 ) b O 1 / 2 SiMe2Vi, Me3SiO 1 / 2 (MeViSiO 1 / 2 ) b O 1 / 2 SiMe3, ViMe2SiO 1 / 2 (Me2SiO 1 / 2 ) a (MeViSiO 1 / 2 ) b O 1 / 2 SiMe2Vi, HexMe2SiO 1 / 2 (Me2SiO 1 / 2 ) a O 1 / 2 SiMe2Hex, HexMe2SiO 1 / 2 (MeHexSiO 1 / 2 ) b O 1 / 2 SiMe2Hex, Me3SiO 1 / 2 (MeHexSiO 1 / 2 ) b O 1 / 2 SiMe3, and HexMe2SiO 1 / 2 (Me2SiO 1 / 2 ) a (MeHexSiO 1 / 2 ) b O 1 / 2 SiMe2Hex, and any combination of any one or more polyorganosiloxanes selected from the group consisting of, wherein Me, Vi and Hex represent methyl, vinyl and hexenyl, respectively, and a and b represent the average number of relevant siloxane units per molecule, and the viscosity of the polyorganosiloxane is selected to be 0.001 Pascal-seconds (Pa*s) or more and 100,000 Pa*s or less at 25 degrees Celsius (°C) when measured by the viscosity test method presented below prior to the examples.

[0030] The unsaturated organopolysiloxane is typically present at a concentration of 15% by weight or more, preferably 20% by weight or more, based on the weight of the composition, and simultaneously typically at a concentration of 98% by weight or less, more typically 95% by weight or less, 90% by weight or less, 75% by weight or less, and even 50% by weight or less. In terms of the solid content (excluding the solvent), the amount of the unsaturated organopolysiloxane is typically 30% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more of the solid weight of the composition (the composition excluding the solvent), and simultaneously typically 99% by weight or less, preferably 97% by weight or less, more preferably 93% by weight or less.

[0031] The unsaturated anhydride compound has both an anhydride functional group and a carbon-carbon double bond or triple bond. Examples of suitable unsaturated anhydride compounds include maleic anhydride, substituted maleic anhydride, alkenyl succinic anhydride, polyisobutenyl succinic anhydride, citraconic anhydride, bromomaleic anhydride, crotonic anhydride, diphenic anhydride, isatoic anhydride, itaconic anhydride, phenylmaleic anhydride, nadic anhydride, 3-(but-3-enyl)-1,2,3,6-tetrahydrophthalic anhydride, and cis-1,2,3,6-tetrahydrophthalic anhydride, phenylsuccinic anhydride, and unsaturated anhydrides characterized by a crosslinked heterocyclic structure (e.g., bicyclooctenedicarboxylic anhydride such as CAS 6708-37-8, bicyclooctenetetracarboxylic dianhydride such as bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (CAS 1719-83-1), ethenocyclobutabenzo[f]furan-trione such as CAS 55054-47-2, and ethenocycloheptafuran-dione such as CAS 5650-01-1, and their isomeric variants). Optionally, any one or any combination of two or more selected from the group consisting of these is mentioned. Desirably, the unsaturated anhydride is selected from maleic anhydride and substituted maleic anhydride. Substituted maleic anhydride is maleic anhydride in which one or both hydrogen atoms on the carbon of the carbon-carbon double bond are replaced by another moiety such as a hydrocarbon or a substituted hydrocarbon. Desirably, the reactive composition does not contain phthalic anhydride.

[0032] The amount of the unsaturated anhydride generally exists at a concentration of 0.1 mol or more, 0.25 mol or more, 0.5 mol or more per mole of the pendant ethylenically unsaturated group in the unsaturated polyorganosiloxane, and at the same time, typically exists at a concentration of 10 mol or less, 5 mol or less, and further 1.5 mol or less.

[0033] The free radical initiator can be, for example, any one or a combination of two or more components selected from the group consisting of benzoyl peroxide, tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, peracetic acid, cyclohexanone peroxide, cumene hydroperoxide, tert-butyl peroxide, tert-butyl hydroperoxide, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azodi(2-methylbutyronitrile) (AMBN), tert-amyl peroxybenzoate, tert-butyl peracetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, cumene hydroperoxide and potassium persulfate. The amount of the free radical initiator is typically 0.01% by weight or more, 0.15% by weight or more, and further 0.2% by weight or more based on the weight of the composition, and at the same time is typically 10% by weight or less, preferably 5% by weight or less, and can be 3% by weight or less.

[0034] The photoinitiator can be any one or any combination of two or more selected from the group consisting of, for example, onium salts, nitrobenzyl sulfonate esters, diaryliodonium salts of sulfonic acids, triarylsulfonium salts of sulfonic acids, diaryliodonium salts of boronic acids, triarylsulfonium salts of boronic acids, bis-diaryliodonium salts (such as bis(dodecylphenyl)iodonium hexafluoroarsenate and bis(dodecylphenyl)iodonium hexafluoroantimonate), dialkylphenyl iodonium hexafluoroantimonate, diaryliodonium salts of sulfonic acids, triarylsulfonium salts of sulfonic acids, diaryliodonium salts of boronic acids, and triarylsulfonium salts of boronic acids. Preferred diaryliodonium salts of sulfonic acids are selected from diaryliodonium salts of perfluoroalkylsulfonic acids and diaryliodonium salts of arylsulfonic acids. Preferred diaryliodonium salts of perfluoroalkylsulfonic acids include diaryliodonium salts of perfluorobutanesulfonic acid, diaryliodonium salts of perfluoroethanesulfonic acid, diaryliodonium salts of perfluorooctanesulfonic acid, and diaryliodonium salts of trifluoromethanesulfonic acid. Preferred diaryliodonium salts of arylsulfonic acids include diaryliodonium salts of paratoluenesulfonic acid, diaryliodonium salts of dodecylbenzenesulfonic acid, diaryliodonium salts of benzenesulfonic acid, and diaryliodonium salts of 3-nitrobenzenesulfonic acid. Preferred triarylsulfonium salts of sulfonic acids are selected from triarylsulfonium salts of perfluoroalkylsulfonic acids or triarylsulfonium salts of arylsulfonic acids. Preferred triarylsulfonium salts of perfluoroalkylsulfonic acids include triarylsulfonium salts of perfluorobutanesulfonic acid, triarylsulfonium salts of perfluoroethanesulfonic acid, triarylsulfonium salts of perfluorooctanesulfonic acid, and triarylsulfonium salts of trifluoromethanesulfonic acid.Preferred triarylsulfonium salts of arylsulfonic acid include triarylsulfonium salts of para-toluenesulfonic acid, triarylsulfonium salts of dodecylbenzenesulfonic acid, triarylsulfonium salts of benzenesulfonic acid, and triarylsulfonium salts of 3-nitrobenzenesulfonic acid. Preferred diaryliodonium salts of boronic acid include diaryliodonium salts of perhaloarylboronic acid, and preferred triarylsulfonium salts of boronic acid are triarylsulfonium salts of perhaloarylboronic acid.

[0035] The total concentration of the free radical initiator and the photoinitiator is typically 0.01 wt% or more, 0.1 wt% or more, 0.15 wt% or more, 0.2 wt% or more, 0.4 wt% or more, 0.6 wt% or more, 0.8 wt% or more, or even 1.0 wt% or more, and at the same time is typically 10 wt% or less, 5 wt% or less, or preferably 4 wt% or less, based on the total weight of the unsaturated polyorganosiloxane, the unsaturated anhydride and the solvent.

[0036] The solvent is not essential, but it is desirable that it is a liquid (at 25 °C) that dissolves at least one, preferably all, of the components of the reactive composition.

[0037] Preferably, the solvent is an aromatic solvent having an alpha hydrogen atom. An aromatic solvent having an alpha hydrogen atom is, in its broadest sense, any aromatic solvent having a hydrogen bonded to a non-aromatic carbon, where the non-aromatic carbon is bonded to a carbon in an aromatic ring. The non-aromatic carbon is not a component of the aromatic ring. Examples of aromatic solvents having an alpha hydrogen include toluene, ethylbenzene, 1,2-dimethylbenzene (o-xylene), 1,3-dimethylbenzene (m-xylene), 1,4-dimethylbenzene (p-xylene), 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,3-trimethylbenzene, and any one or combination of two or more selected from the group consisting of substitutional forms of any of these. Preferably, the aromatic solvent is selected from toluene, xylene isomers, and combinations thereof.

[0038] The solvent can be dried prior to use by common drying procedures such as contacting the solvent with molecular sieves, silica gel, or other chemical desiccants, or sparging with a dry inert gas.

[0039] Typically, the concentration of the solvent is 5 wt% or more, preferably 10 wt% or more, and may be 15 wt% or more, but is typically 95 wt% or less, 90 wt% or less, or even 60 wt% or less, based on the weight of the composition.

[0040] By triggering a free radical initiator and / or a photoinitiator, the reaction of the reactive composition is initiated to form the polyorganosiloxane of the present invention. By triggering, the free radical initiator and / or the photoinitiator form free radicals. Methods for triggering free radical initiators and photoinitiators are known in the art. In many cases, the free radical initiator is triggered by heating it to a temperature higher than the trigger temperature, and the photoinitiator is exposed to a specific trigger wavelength of radiation-triggered photoinitiator. Multicomponent schemes that trigger upon mixing without heat or irradiation are also possible, such as using a redox catalyst for the free radical initiator.

[0041] The polyorganosiloxane of the present invention is particularly useful as a component in a curable composition comprising (a) a polyorganosiloxane having anhydride functional groups and aromatic functional groups, and (b) an organopolysiloxane containing on average at least two silicon-bonded amines or two silicon-bonded epoxy groups per molecule. Desirably, the curable composition contains a molar ratio of anhydride functional groups to either amine or epoxy groups that is 10 or less, 5 or less, 2 or less, 1.5 or less, 1.2 or less, or even 1 or less, and is typically 0.1 or more, 0.2 or more, 0.5 or more, or 0.7 or more.

[0042] Component (b) can be linear, branched or resinous. The amine and epoxy groups typically have two or more carbon atoms and generally have 18 or fewer, and even 15 or fewer, carbon atoms. The amine and epoxy groups are pendant from the silicon atom and can be terminally pendant (extending from the silicon atom of the M siloxane unit).

[0043] Examples of suitable amine groups that can be pendants include primary amine groups such as 3-aminopropyl, 2-aminoethyl, aminomethyl, 6-aminohexyl, 11-aminoundecyl, 3-(N-allylamino)propyl, N-(2-aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3-aminoisobutyl, p-aminophenyl, 2-ethylpyridine, and 3-propylpyrrole groups. In some embodiments, the amine group can be selected from tertiary amine groups such as bis(2-hydroxyethyl)-3-aminopropyl, N,N-dimethyl-3-aminopropyl, N,N-diethyl-3-aminopropyl, and N,N-diethylaminomethyl. In some embodiments, the amine group can be selected from aminoalkyl groups having the formula R’-(NH-A’) q -NH-A-, where A and A’ are each independently a linear or branched alkylene group having 1 to 6 carbon atoms and optionally containing an ether bond, q = 0 to 4, and R’ is hydrogen or an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms. Examples of such aminoalkyl groups include, but are not limited to, -(CH2)3NH2, -(CH2)4NH2, -(CH2)3NH(CH2)2NH2, -CH2CH(CH3)CH2NH(CH2)2NH2, -(CH2)3NHCH2CH2NH(CH2)2NH2, -CH2CH(CH3)CH2NH(CH2)3NH2, -(CH2)3NH(CH2)4NH2, and -(CH2)3O(CH2)2NH2.

[0044] Examples of suitable epoxy groups that can be pendants include examples where the epoxy group is bonded to the silicon atom via an alkylene group so that these epoxy groups are not directly bonded to the silicon atom. These groups are exemplified by 3-(glycidoxy)propyl group, 2-(glycidoxycarbonyl)propyl group, 2-(3,4-epoxycyclohexyl)ethyl group, and 2-(4-methyl-3,4-epoxycyclohexyl)propyl group. Further examples of epoxy groups include any C1-15 organic groups as described above that contain an epoxy group. For example, 2,3-epoxypropyl or 2,3-epoxypropoxy group can be a suitable epoxy functional group.

[0045] In addition to those described above, the curable composition can contain or not contain any one component or a combination of two or more components selected from the group consisting of stabilizers, reinforcing fillers, extender fillers, siloxane resins, silane coupling agents, pigments, dyes, adhesion promoters, curing catalysts, accelerators, and inhibitors.

[0046] Characteristic Evaluation Test Method The characteristics of the material are evaluated using the following test methods.

[0047] Molecular weight. The number average molecular weight (Mn) and polydispersity (Mw / Mn) are determined by gel permeation chromatography (GPC). The sample is prepared in tetrahydrofuran at a concentration of 10 milligrams per milliliter, solvated for 1 hour with occasional shaking, and filtered through a 0.45 micrometer polytetrafluoroethylene syringe filter prior to analysis. A 100 microliter injection volume is used and data is collected for 25 minutes. The chromatography apparatus consists of a Waters 2695 separation module and a Waters 2410 differential refractometer. Two (300 millimeter × 7.5 millimeter) Polymer Laboratories PLgel 5 micrometer Mixed-C columns (molecular weight separation range 200 - 2,000,000) provided by a PLgel 5 micrometer guard column (50 millimeter x 7.5 millimeter) are used. Analysis is performed using certified grid tetrahydrofuran flowing at 1.0 milliliter per minute as the eluent, and the column and detector are maintained at 35 °C. Data collection and analysis are performed using ThermoLabsystems Atlas 8.3 chromatography software and Polymer Laboratories Cirrus 2.0 GPC software. The molecular weight average is determined relative to a third-order polynomial calibration curve created using polystyrene standards covering a molecular weight range of 580 to 2,300,000 grams per mole.

[0048] Attenuated total reflection infrared (ATR-IR) spectroscopy. The sample is tested at 23 °C using a Nicolet 6700 Fourier transform infrared (FTIR) spectrometer equipped with a Smart Miracle accessory having a zinc selenide crystal. Liquid samples are tested by placing 2 drops of the sample on the crystal to ensure complete coating of the crystal through 32 scans. Solid samples are tested by placing the solid sample in contact with the crystal. When determining the spectral quality by previewing, the contact pressure is kept to a minimum to establish complete crystal contact in order to maximize the signal-to-noise ratio.

[0049] Viscosity. The viscosity of the sample is determined using an Anton Paar MCR-301 cone-plate rheometer (having a 25-millimeter diameter cone at an angle of 1.988° and a truncation of 104 micrometers). For all reaction products in which a solvent is present, first, a small amount of the sample is dried in an aluminum weighing dish at 150 °C for 2 hours in a convection oven to remove the solvent before testing. At intervals of five data points per digit, the shear rate is gradually increased from 0.1 to 500 (s -1 ) per second and then decreased from 500 to 0.1 s -1 per second while measuring the shear viscosity data for a given temperature to evaluate hysteresis. The time interval for each data point is 10 seconds to ensure that the steady-state viscosity is achieved. Since the sample has little shear rate dependence over this range, the zero-shear viscosity at 25 °C is the value at 10 s -1 even for a low-viscosity control sample where there is a good signal-to-noise ratio. Using a Peltier heating device that is purged with a gentle sweep of dry compressed air and automatically corrects for the thermal expansion of the tool, the temperature dependence of the viscosity is probed using a thermal gradient from 25 °C to 150 °C at a rate of 5 °C per minute. Points are measured at intervals of approximately 4 °C at a shear rate of 10 s -1 . Once 150 °C is reached, the gradient is reversed and the measurements are repeated while cooling at the same rate of 5 °C per minute to test for hysteresis.

[0050] Nuclear Magnetic Resonance Spectroscopy (NMR). 1 For 1H NMR spectroscopy, the sample is prepared by dissolving approximately 740 milligrams of the sample in 3 grams of deuterated chloroform. Optionally, 0.2 wt% of dry acetonitrile is included as an internal reference. The solution is mixed with a vortex mixer and 1 gram of the solution is transferred to a 5-millimeter glass proton NMR tube and cap. All NMR analyses are performed at 25 °C using an Agilent Technologies 400 megahertz NMR spectrometer equipped with a Varian 7600AS NMR autosampler.

[0051] 1313C NMR spectroscopy and 29 For 29Si NMR spectroscopy, a sample of approximately 740 milligrams is prepared by dissolving it in 3 grams of deuterated chloroform. 2 grams of the resulting solution is mixed with 0.02 mol of Cr(acac)3 at 60 volume percent in deuterated chloroform and analyzed using a Mercury 400 megahertz NMR spectrometer in a 15 millimeter silicon-free Wilmad polytetrafluoroethylene tube. The relaxation time is 13 seconds and the number of accumulations is 256.

[0052] Quantification of the entire NMR spectrum is performed with a fixed integration limit between spectra in the series after applying a uniform phase, internal reference, and baseline correction procedure using the manual integration function of ACD Spectrus Process 2015. 1 The conversion of vinyl is determined by comparing the normalized integral values of the Si-CH=CH2 triplet (5.75, 5.93, 6.12 ppm) in the unreacted (t = 0) sample obtained by 1H NMR with the reaction products obtained at various times, or by 29Si NMR using the integral peaks in the M Vi (-4 ppm) and D Vi (-36 ppm) regions in a similar manner.

[0053] Non-volatile content (NVC). To determine the exact initial weight (Wi), place 2 grams of the sample in a pre-weighed clean aluminum dish on a four-digit balance. Place the sample either (a) in a forced convection oven at 150 °C for 2 hours (forced air drying), or (b) in a vacuum oven at 90 °C for 2 hours under a full vacuum at a pressure of less than 10 torr (10 millimeters of mercury column) (vacuum drying). Cool the sample to ambient temperature and measure the final weight (Wf). Determine the NVC using the following formula. NVC (wt%) = (1 - (Wi - Wf) / (Wi)) * 100%

[0054] Water vapor sorption method. Samples of 6 - 10 milligrams dried at 150 °C for 2 hours in a forced air convection oven are placed on a microbalance in a vapor sorption analyzer (TA Instruments VTI - SA+). After first undergoing a drying step at 80 °C for 3 hours, the sample is exposed to a controlled mixture of dry nitrogen gas stream and humid water vapor stream generated by sweeping a nitrogen gas stream over a heated solvent cell filled with deionized water to produce various partial pressures of water vapor relative to saturation within the range of 0.05 - 0.90 (5% - 90% relative humidity) at a constant temperature of 20 °C or 40 °C. After the drying step, the relative pressure (RP) is increased isothermally at 2 - hour intervals to 0.02, 0.2, 0.4, 0.6, 0.8 (for the 40 °C isotherm) and 0.9 (for the 20 °C isotherm) to measure the time - dependent (non - equilibrium) uptake weight of water at each relative pressure and record the adsorption profile. Immediately, the sample is returned at 2 - hour intervals from the maximum relative pressure step to relative pressures of 0.6, 0.4, 0.2 and 0.02 to measure the temporary uptake weight of water and record the desorption profile. The difference in the uptake weight of water between the adsorption and desorption curves at the relative pressure is calculated to obtain an estimate of the degree of hysteresis exhibited by the sample. The hysteresis is due to the hydrolysis of the grafted anhydride functional groups present in the sample.

[0055] Gas chromatography (GC)-mass spectrometry (MS) analysis. For GC analysis, a Thermotrace 1310 gas chromatograph equipped with a DB-5 column was used. The injector temperature was 275 °C, the temperature gradient: (held at 35 °C for 2 minutes, increased to 300 °C at 10 °C per minute, and held for 2 minutes), the MS transfer line temperature: (MS - 280 °C, GC1 - 280 °C, GC2 - 280 °C), liquid injection, injection volume 0.1 microliter, split ratio 50, and flow rate 1.00 milliliter / minute. For MS analysis, a Thermo GC-Qexactive device was used. The scan types were full scan and dd product ion scan (dd scan for Cl only), the ionization types were El, Cl (pure ammonia gas), 50 - 700 m / z scan range, 60000 resolution, profile spectrum data type, 1E6 AGC target, maximum injection time 100 milliseconds, reagent gas flow 1.5 milliliters / minute, 70 eV (EI) 120 eV (CI) energy, and filament on delay of 2.0 minutes or 8.0 minutes.

Example

[0056] Table 1 shows the polymers for use in the following Examples (Ex) and Comparative Examples (Comp Ex). Tetrahydrofuran, HPLC grade (THF), deuterated chloroform (CDCl3), benzoyl peroxide (BPO), maleic anhydride (MA), methylene chloride, azobisisobutyronitrile (AIBN), and 2,2'-azodi(2-methylbutyronitrile (AMBN (Vazo 67)) are available from Sigma-Aldrich. Anhydrous toluene and meta-xylene (m-xylene) are from Acros. Methyl methyl isobutyl ketone (MIBK), para-xylene (p-xylene), and methyl ethyl ketone (MEK) are available from MilliporeSigma.

Table 1

[0057] Examples 1 - 2: Small polysiloxane (MM vi ) Example 1. MMvi (0.50 g, 2.9 mmol) and MA (0.28 g, 2.9 mmol) are combined and heated to 60 °C in chlorobenzene (6.0 g). 0.07 g of BPO is added and the mixture is heated at 120 °C for 30 minutes with stirring. It is held at 120 °C for 90 minutes and then cooled. The reaction mixture is dried under a nitrogen stream to remove volatile substances and the solvent, and reconstituted to approximately the same solvent level in dichloromethane. It is loaded into an autosampler tray for GC-MS analysis. The chromatograph shows main peaks and minor peaks with exact masses corresponding to the following respective assignable structures for siloxane-containing species based on the mass spectrum. Main product: [Chemical formula] By-product: [Chemical formula]

[0058] Example 2. Example 1 is repeated except that 6.0 g of p-xylene is used instead of 6.0 g of chlorobenzene. GC-MS analysis reveals that there are two main products and two by-products. Main product: [Chemical formula] [Chemical formula] By-product: [Chemical formula] [Chemical formula]

[0059] Comparative Example A and Examples 3 - 4: Vi-PDMS1 reaction Comparative Example A: Vi-PDMS1 containing MA in a non-aromatic solvent. Prepare a reactor assembly equipped with a 500 milliliter (mL) three-necked flask with a baffle, an overhead stirrer, a thermocouple and a temperature controller, a nitrogen inlet and a nitrogen outlet bubbler. Dry the flask in an oven. Add 200 g of Vi-PDMS1 to the flask under nitrogen and purge for 1 hour while heating to 60 °C. Add 2.04 g of MA and 8 g of MIBK, followed by 4.24 g of BPO, and increase the stirring speed to 500 revolutions per minute. The reaction mixture is heated, the viscosity increases, and it reaches 118 °C in 15 minutes. The reaction mixture gels completely in 17 minutes. This result shows that a cross-linking reaction occurs with only MA and Vi-PDMS1.

[0060] Example 3: Vi-PDMS1 containing MA in p-xylene. Prepare a reactor assembly equipped with a 500 milliliter (mL) three-necked flask with a baffle, an overhead stirrer, a thermocouple and a temperature controller, a nitrogen inlet and a nitrogen outlet bubbler. Dry the flask in an oven. Add 60.0 g of Vi-PDMS1 to the flask under nitrogen and purge for 1 hour while heating to 60 °C. Add 1.23 g of MA and 140 g of p-xylene and homogenize the mixture while stirring at 300 revolutions per minute. Add 1.21 g of BPO and increase the stirring speed to 500 revolutions per minute. Heat the mixture to 120 °C, hold at that temperature for 90 minutes, and then cool to room temperature. Remove most of the p-xylene using a rotary evaporator under vacuum. Transfer the product to a dried 125 mL glass bottle and dry further under a stream of dry nitrogen at 110 °C.

[0061] 1 1H NMR shows that the product distribution is 50% xylyl-MAH adduct (MM vi which is similar to the main product (a) from Example 2, except having the Vi-PDMS1 remainder instead of the remainder), 44% residual vinyl and approximately 6% unassigned product. The conversion is relative to the integration of the SiMe2 protons on the parent Vi-PDMS1.

[0062] Example 4: Vi-PDMS1 containing MA in toluene. Add 199.4 g of dry toluene, 40.0 g of Vi-PDMS1 and 10.93 g of MA to a clean and dry 500 mL round-bottom three-necked flask with a baffle and equipped with a water-cooled reflux condenser. Purge the headspace of the reactor with a dry nitrogen stream just sufficient to maintain a slight positive pressure. Stir the contents at 150 revolutions per minute with a polytetrafluoroethylene blade. Monitor the temperature of the reaction solution with a dual independent K-type thermocouple immersed in the reaction mixture. Heat the contents to 70 °C to completely dissolve the MA. Remove a 203 mL sample of the reaction mixture. Add 8.44 g of BPO to the flask. Heat the reaction mixture to reflux at 110 °C and maintain for 3 hours while periodically taking samples of the reaction solution. Cool the solution to 25 °C while maintaining the nitrogen purge. Evaluate the final sample by GPC, ATR-IR, rheometry and NMR for molecular weight. Compare the results in Table 2 with the results of ViPDMS1 alone. Using the dry film of the reaction product, heat a few drops of the sample on a glass slide with a hot air gun and contact the film with an IR crystal for infrared analysis. Compare the IR results with a reference sample of neat MA dissolved in methylene chloride and show the results in Table 3.

[0063] The results in Table 3 show that vinyl groups are lost from both the MA reagent and the Vi-PDMS1 reagent, and a significant amount of -C=O groups corresponding to grafting of MA are incorporated. This result, combined with the results in Table 2 showing a well-controlled shift in the number average molecular weight and molecular weight distribution polydispersity index, and a large 3400-fold increase in viscosity imbalance, is evidence of the disappearance of M(vi) groups with the formation of MR groups. 29 It is shown that by Si, a significant modification of the structure and properties of the vinyl-functional siloxane is achieved by maleic anhydride and aryl functionalization with the composition of the present invention.

Table 2

Table 3

[0064] Example 5: Vi-PDMS1 containing MA in m-xylene Into a clean and dry 250 mL round-bottom three-necked flask with baffles, baked in an oven at 80 °C, add 64.99 g of dry m-xylene, 35.00 g of Vi-PDMS1 and 9.723 g of MA. Attach a water-cooled reflux condenser to the flask. Purge the headspace of the reactor with a dry nitrogen stream just sufficient to maintain a slight positive pressure. Stir the contents at 150 revolutions per minute (rpm) with a polytetrafluoroethylene blade. Monitor the temperature of the reaction solution with a dual independent K-type thermocouple immersed in the reaction mixture. Heat the contents to 60 °C to completely dissolve the MA. Withdraw a 6.65 mL sample of the reaction mixture. Add 2.239 g of BPO to the flask and increase the stirring speed to 200 rpm. Heat the reaction mixture to reflux at 120 °C and maintain for 2 hours while periodically taking samples of the reaction solution. Cool the solution to 25 °C while maintaining the nitrogen purge. Evaluate the final sample by GPC, rheometry and water vapor adsorption analysis for molecular weight. The resulting product was stripped in a rotary evaporator at 150 °C to remove the solvent. The resulting dry reaction product was a viscous liquid having a zero-shear viscosity of 11350 mPa*s at 25 °C, which was significantly higher than the viscosity of the Vi-PDMS1 starting material (2 mPa*s). It should be noted that this Vi-PDMS1 has the same composition as that used in Example 3, Example 4 and Comparative Example A, but is from a different batch. The differences in viscosity and molecular weight distribution reflect the variation between batches in Vi-PDMS1. Despite the significant increase in viscosity, GPC showed that the Mn shift was much milder, increasing to 1410 Da (from 869 Da of Vi-PDMS1), and Mw / Mn increased to 2.3 (from 1.5 of Vi-PDMS1). Measure water vapor sorption and hysteresis at 40 °C. The dried reaction product had a water vapor adsorption (wt%) of 1.539 wt% at 0.8 RP and 40 °C and showed significant hysteresis between the adsorption and desorption steps. In contrast, the unreacted Vi-PDMS1 starting material showed much less water adsorption (0.099 wt% at 0.8 RP and 40 °C) and no significant hysteresis. These results of the property evaluations confirm the success of the functionalization of V-PDMS1 to the polymers of the present invention.

[0065] Example 6: Vi-PDMS1 containing MA in m-xylene with a reduced vinyl ratio. Into a clean and dry 250 mL round-bottom three-necked flask with baffles, baked in an oven at 80 °C, add 65.04 g of dry m-xylene, 35.01 g of Vi-PDMS1, and 4.972 g of MA corresponding to half of the molar ratio of MA:vinyl groups present in Vi-PDMS3 used in Example 29 to target a lower MA grafting level. Attach a water-cooled reflux condenser to the flask. Purge the headspace of the reactor with a dry nitrogen stream just sufficient to maintain a slight positive pressure. Stir the contents at 150 revolutions per minute with a polytetrafluoroethylene blade. Monitor the temperature of the reaction solution with a dual independent K-type thermocouple immersed in the reaction mixture. Heat the contents to 60 °C to completely dissolve the MA. Withdraw a 6.65 mL sample of the reaction mixture. Add 2.146 g of BPO to the flask and increase the stirring speed to 200 rpm. Heat the reaction mixture to reflux at 120 °C and maintain for 2 hours while periodically taking samples of the reaction solution. Cool the solution to 25 °C while maintaining the nitrogen purge. Evaluate the final sample by GPC, rheometry, and water vapor sorption analysis for molecular weight. Strip the resulting product in a rotary evaporator at 150 °C to remove the solvent. The resulting dry reaction product is a viscous liquid having a zero-shear viscosity of 1424 mPa*s at 25 °C, which is significantly higher than the viscosity of the Vi-PDMS1 starting material (2 mPa*s), but lower than the viscosity of Example 5. It should be noted that this Vi-PDMS1 is from the same batch as that used in Example 5. The differences in viscosity and molecular weight distribution reflect the batch-to-batch variation in Vi-PDMS1. Despite the increase in viscosity, GPC showed that the Mn shift was much milder, increasing to 1370 Da (from 869 Da of Vi-PDMS1), and Mw / Mn increased to 2.15 (from 1.5 of Vi-PDMS1). Measure water vapor sorption and hysteresis at 40 °C. The dry reaction product had a water vapor sorption of 0.878 wt% (wt%) at 0.8 RP and 40 °C and showed significant hysteresis between the adsorption and desorption steps. In contrast, the unreacted Vi-PDMS1 starting material showed much less water adsorption (0.099 wt% at 0.8 RP and 40 °C) and no significant hysteresis.The water vapor adsorption level is intermediate between that of Example 29 and the unreacted Vi-PDMS1 sample, consistent with the expected decrease in the grafting level of the MA groups. These results of the characterization confirm the successful functionalization of Vi-PDMS1 onto the polymers of the present invention and further demonstrate the ability of the method of the present invention to control the level of functionalization by adjusting the molar ratio of MA:vinyl groups present on the unsaturated polyorganosiloxane.

[0066] Comparative Example B and Example 7: Vi-PDMS2 reaction Example 7: Vi-PDMS2 containing MA and m-xylene. Add 80.0 g of dry m-xylene, 20.0 g of Vi-PDMS2 and 0.855 g of MA to a clean and dry 250 mL round-bottom three-necked flask with baffles, baked in an oven at 80 °C. Attach a water-cooled reflux condenser to the flask. Purge the headspace of the reactor with a small stream of dry nitrogen maintaining a slight positive pressure. Stir the contents with a polytetrafluoroethylene blade stirrer at 150 revolutions per minute. Monitor the temperature with a Type K thermocouple immersed in the reaction mixture. Heat the contents of the flask to 60 °C to dissolve the MA. Take out 2 - 3 mL of the sample mixture and then add 1.05 g of BPO. Heat the contents to 120 °C and periodically take 2 - 3 mL of the test sample solution while maintaining the temperature at that level for 4 hours. Cut off the heat and cool to 25 °C while maintaining the nitrogen purge. Characterize the final test sample by GPC, ATR-IR, rheometry and NMR. The results are shown in Table 4. Also, characterize the final test sample by NVC, compare the results with Vi-PDMS2, and the results are shown in Table 5.

[0067] Comparative Example B: Vi-PDMS2 in m-xylene without MA. Repeat Example 7 except without MA. The obtained sample is dried and characterized by rheometry. Despite heating at 110 °C for 4 hours in the presence of BPO, the obtained sample did not show a significant increase in viscosity with respect to unreacted Vi-PDMS2. This is confirmed by rheometry showing Newtonian behavior with viscosities of 423 mPa*s at 25 °C and 84.5 mPa*s at 150 °C, representing a difference of less than 2.5% with respect to the unreacted Vi-PDMS2 starting material. This is consistent with GPC molecular weight analysis showing no significant change in molecular weight or polydispersity index over the course of the reaction.

Table 4

Table 5

[0068] The IR of Example 7 shows the incorporation of a -C=O stretching peak related to the incorporation of maleic anhydride at 1786 cm -1 This indicates that it is the anhydride that is incorporated into the polymer product, as GC-MS does not consider the anhydride peak since free MA is removed under dry conditions. Further evidence for the formation of the product of the present invention includes a six-fold increase in viscosity at 25 °C and NMR evidence for the disappearance of the M(vi) and D(vi) groups with respect to Vi-PDMS2. The NVC data in Table 5 further confirms the presence of anhydride functional groups in Example 7.

[0069] Examples 8 - 14: Use of branched polysiloxane (resin) Example 8. Add 180.0 g of dry toluene, 20.0 g of Vi-MQ1, and 1.38 g of MA to a clean and dry 500 mL Morton-type round-bottom four-necked flask with baffles, and bake it in an oven at 80 °C. Attach a water-cooled reflux condenser to the flask, and purge the headspace with a nitrogen stream to create a slight pressure. Stir the contents of the flask at 200 revolutions per minute with a polytetrafluoroethylene blade. Monitor and maintain the temperature with a K-type thermocouple connected to a Cole-Parmer digital programmable temperature controller. Heat the contents of the flask to 60 °C to dissolve mA, and then remove 2 - 3 mL of the sample. Add 8.06 g of BPO. Heat under reflux for 4 hours while periodically collecting 2 - 3 mL of the sample (110 °C when using a toluene solvent, 120 °C when using an m-xylene solvent). Cool all the contents of the flask to 25 °C while maintaining the nitrogen purge. Evaluate the characteristics of the final sample according to the above characteristic evaluation test.

[0070] Examples 9 - 13. Repeat Example 8 using the amounts of reactants described in Table 6 in a 250 mL Morton-type round-bottom four-necked flask with baffles.

[0071] Examples 14 - 21. Repeat Example 9 except using a 73.9 wt% Vi-MQ2 solution instead of Vi-MQ1 and using the amounts of the other agents described in Table 6.

Table 6

[0072] Table 7 shows the molecular weights and %M vi conversion rate ( 1 by 1H NMR) for Examples 8 - 14. The results show that, in line with the formation of the polyorganosiloxane of the present invention, M vi is consumed and the molecular weight increases slightly without crosslinking or gelation.

Table 7

Table 8

[0073] As is clear from the data in Table 8, the change in Mn and the increase in water vapor sorption in Examples 15 to 21 are consistent with the formation of the substituted polyorganosiloxane according to the present invention.

[0074] Furthermore, the initial polymers of Examples 8 to 21 do not form a film upon heating, but the reaction products form a film after heating, further indicating that the resinous polyorganosiloxane is converted to the substituted polyorganosiloxane of the present invention.

[0075] Example 22: Hexanyl-functional polyorganosiloxane Repeat Example 7 except that 80.0 g of hex-PDMS is used instead of Vi-PDMS2, and 0.99 g of MA and 2.06 g of BPO are used.

[0076] At T = 0 (before reaction), the Mn of the polymer is 11690 g / mol, Mw / Mn is 2.44, water vapor sorption is 0.303, and hysteresis is -0.043. The Mn of the final product is 16188 g / mol, Mw / Mn is 27.0, water vapor sorption is 0.794, and hysteresis is 0.212. Water vapor sorption and hysteresis are measured at 0.8 RP and 40 °C. The significant change in Mn of the final product relative to the starting polymer and the significant increase in water vapor adsorption indicate the formation of the polymer of the present invention. The significant hysteresis indicates hydrolysis of the anhydride functional group.

[0077] Example 23: Cyclosiloxane Repeat Example 7 except that a 30.0 g mixture of 99 wt% Vi-MCS1, 0.5 wt% pentamethylpentavinylcyclopentasiloxane, and 0.5 wt% trimethyltrivinylcyclotrisiloxane is used instead of Vi-PDMS2, and 8.54 g of MA and 2.22 g of BPO are used.

[0078] Vi-MCS1 is too volatile to allow for property evaluation, but at T = 0.25 h of reaction, the polymer has a Mn of 2800 g / mol and a Mw / Mn of 3.05. At T = 0.5 h of reaction, the polymer has a Mn of 3730 g / mol and a Mw / Mn of 12.9, and has a water vapor sorption of 0.528 and a hysteresis (relative to PDMS) of 0.54. Measure water vapor sorption and hysteresis at 0.9 RP and 40 °C, and hysteresis at 0.2 RP and 20 °C. The increase in Mn during the reaction indicates that the reaction is occurring. The water vapor sorption and hysteresis values indicate the incorporation of anhydride functional groups consistent with the formation of the polymers of the present invention.

[0079] Example 24: Vi-PDMS3 containing MA in m-xylene. Into a clean and dry 2-liter round-bottom three-necked flask with baffles, baked in an oven at 80 °C, add 900.2 g of dry m-xylene, 600.0 g of Vi-PDMS3 and 18.31 g of MA. Attach a water-cooled reflux condenser to the flask. Purge the headspace of the reactor with a dry nitrogen stream sufficient to maintain a slight positive pressure. Stir the contents at 190 revolutions per minute with a polytetrafluoroethylene blade. Monitor the temperature of the reaction solution with a dual independent K-type thermocouple immersed in the reaction mixture. Heat the contents to 70 °C to completely dissolve the MA. Remove a 25.71 g sample of the reaction mixture. Add 38.93 g of BPO to the flask. Heat the reaction mixture to reflux at 120 °C and maintain for 2 hours while periodically taking samples of the reaction solution. Cool the solution to 25 °C while maintaining the nitrogen purge. Evaluate the final sample by GPC, ATR-IR, rheometry and NMR for molecular weight. Strip the resulting product in a rotary evaporator at 150 °C to remove the solvent. The resulting dry reaction product is a viscous liquid having a zero-shear viscosity of 3030 mPa*s at 25 °C, which was significantly higher than the viscosity of the Vi-PDMS3 starting material (450 mPa*s). 1H NMR revealed a conversion of approximately 70% of the vinyl groups relative to the Vi-PDMS3 starting material. Measure water vapor sorption and hysteresis at 40 °C. The dry reaction product had a water vapor adsorption (wt%) of 0.26 wt% at 0.8 RP and 40 °C and showed significant hysteresis between the adsorption and desorption steps. In contrast, the unreacted Vi-PDMS3 starting material showed much less water adsorption (0.043 wt% at 0.8 RP and 40 °C) and no significant hysteresis. These property evaluation results confirm the success of the functionalization of V-PDMS3 to the polymer of the present invention.

[0080] Example 25: Vi-PDMS3 Containing MA in m-Xylene with Reduced Stoichiometry Into a clean and dry 500 mL round-bottom four-necked Morton flask with baffles, baked in an oven at 80 °C, add 150.1 g of dry m-xylene, 100.0 g of Vi-PDMS3, and 1.525 g of MA corresponding to half of the molar ratio of MA:vinyl groups present in the Vi-PDMS3 used in Example 24 to target a lower MA grafting level. Attach a water-cooled reflux condenser to the flask. Purge the headspace of the reactor with a dry nitrogen stream sufficient to maintain a slight positive pressure. Stir the contents at 120 revolutions per minute with a polytetrafluoroethylene blade. Monitor the temperature of the reaction solution with a dual independent K-type thermocouple immersed in the reaction mixture. Heat the contents to 60 °C to completely dissolve the MA. Remove a 6.64 g sample of the reaction mixture. Add 6.45 g of BPO to the flask. Heat the reaction mixture to reflux at 120 °C and maintain for 2 hours while periodically taking samples of the reaction solution. Cool the solution to 25 °C while maintaining the nitrogen purge. Evaluate the final sample by GPC, ATR-IR, rheometry and NMR for molecular weight. The resulting product was stripped at 150 °C in a rotary evaporator to remove the solvent. The resulting dry reaction product was a viscous liquid having a zero-shear viscosity of 1250 mPa·s at 25 °C, which was significantly higher than the viscosity of the Vi-PDMS3 starting material (450 mPa·s), but lower than that reported in Example 24 carried out at a molar ratio of MA:vinyl groups twice that present in Vi-PDMS3. 1H NMR revealed an approximately 30% conversion of vinyl groups relative to the Vi-PDMS3 starting material. These property evaluation results confirm the successful functionalization of V-PDMS3 to the polymer of the present invention and further demonstrate the ability to control the level of functionalization in the method of the present invention.

[0081] Example 26: Vi-PDMS3 containing MA in m-xylene using a stoichiometry-reduced continuous process. Vi-PDMS3 was fed via an ISCO pump at a flow rate of 4.06 kg per hour (kg / h) corresponding to a residence time of about 5 minutes to a 25 mm Coperion co-rotating twin screw extruder with an L / D of 48, where this feed line was preheated to a set point of 120 °C, the same temperature as the entire extruder barrel, with an oil-based heater. A combination of MA and BPO, pre-diluted to concentrations of 5.6 wt% and 22.4 wt% in a mixture of p-xylene and MEK, where 22.4 wt% of the solvent is MEK, was fed via an HPLC pump at a rate of 0.46 kg / h to a feed port located 20 centimeters (cm) downstream of the Vi-PDMS3 feed port. A screw rotation speed of 400 revolutions per minute (rpm) was used. The resulting dried reaction product was a viscous liquid having a zero-shear viscosity of 949 mPa*s at 25 °C, which was significantly higher than the viscosity of the Vi-PDMS3 starting material (450 mPa*s), and GPC showed only a slight increase of 14% in the number average molecular weight (M n ), and there was little change in the polydispersity (weight average molecular weight divided by number average molecular weight, or "M w / M n "). By 1H NMR, a conversion of about 36% of the vinyl groups relative to the Vi-PDMS3 starting material was revealed. The results of these characterizations demonstrate an embodiment of the method of the present invention that utilizes a continuous production method to produce the polymers of the present invention.

[0082] Example 27: Vi-PDMS3 containing MA in m-xylene using a stoichiometry-reduced continuous process. To a 25 mm Coperion co-rotating twin-screw extruder with an L / D of 48, Vi-PDMS3 was supplied via an ISCO pump such that the total mass flow rate through the extruder was 2.03 kg / h to correspond to a residence time of about 10 minutes. Here, this supply line was preheated to a set point of 140 °C, which is the same temperature as the entire extruder barrel with an oil-based heater. A combination of MA and BPO, which was pre-diluted to concentrations of 5.6 wt% and 22.4 wt% in a mixture of p-xylene and MEK where 22.4 wt% of the solvent was MEK, was supplied at a rate of 0.24 kg / h via an HPLC pump to a supply port located 20 cm downstream of the Vi-PDMS3 supply port. A screw rotation speed of 200 rpm was used. The resulting dried reaction product was a viscous liquid having a zero-shear viscosity of 1167 mPa*s at 25 °C, which was significantly higher than the viscosity (450 mPa*s) of the Vi-PDMS3 starting material. GPC showed only a slight increase of n only 16% in M w / M n and there was little change (2.52) in

[0083] Comparative Example C: Vi-PDMS3 blank using a continuous process. The conditions used in Example 26 were repeated on the same Coperion 25 mm twin-screw extruder, with Vi-PDMS3 supplied via an ISCO pump at a flow rate of 4.54 kg / h, where the feed line was preheated with an oil-based heater to a set point of 120 °C, which was the same temperature as the entire extruder barrel. However, no reagents, initiators, or solvents were added to the downstream injection port. The final sample was evaluated by GPC, rheometry, and NMR for molecular weight. The resulting material was a liquid with a zero-shear viscosity of 455 mPa*s at 25 °C, which was almost unchanged from the viscosity of the Vi-PDMS3 starting material (450 mPa*s). 1H NMR revealed a conversion of approximately 0% of vinyl groups relative to the Vi-PDMS3 starting material, and GPC showed no statistically significant change in the polymer's M n and M w / M n relative to the Vi-PDMS3 starting material. These property evaluation results confirm that the continuous extrusion process itself does not affect Vi-PDMS3 and that the embodiments of the method of the present invention illustrated in Examples 26 and 27 are involved in the production of the polymers of the present invention.

[0084] Example 28. Vi-PDMS4 containing MA in m-xylene. Add 150.2 g of dry m-xylene, 150.00 g of Vi-PDMS4 and 9.22 g of MA to a clean and dry 500 mL round-bottom three-necked flask with baffles, baked in an oven at 80 °C. Attach a water-cooled reflux condenser to the flask. Purge the headspace of the reactor with a dry nitrogen stream sufficient to maintain a slight positive pressure. Stir the contents at 190 revolutions per minute with a polytetrafluoroethylene blade. Monitor the temperature of the reaction solution with a dual independent K-type thermocouple immersed in the reaction mixture. Heat the contents to 70 °C to completely dissolve the MA. Take out 5.0 g of a sample of the reaction mixture. Add 6.30 g of BPO to the flask. Heat the reaction mixture to reflux at 120 °C and maintain for 2 hours while periodically taking samples of the reaction solution. Cool the solution to 25 °C while maintaining the nitrogen purge. Evaluate the final sample by GPC, ATR-IR, rheometry and NMR for molecular weight. Strip the resulting product in a vacuum oven at 90 °C to remove the solvent. The resulting dried reaction product is a viscous liquid having a zero-shear viscosity of 9370 mPa*s at 25 °C, which was significantly higher than the viscosity of the Vi-PDMS4 starting material (61.8 mPa*s). By 1H NMR, about 67% conversion of vinyl groups was revealed relative to the Vi-PDMS4 starting material. Measure water vapor sorption and hysteresis at 40 °C. The dried reaction product had a water vapor adsorption of 1.25 wt% (wt%) at 0.8 RP and 40 °C and showed significant hysteresis between the adsorption and desorption steps. In contrast, the unreacted Vi-PDMS4 starting material showed much less water adsorption (0.054 wt% at 0.8 RP and 40 °C) and no significant hysteresis. These property evaluation results confirm the success of the functionalization of V-PDMS4 to the polymer of the present invention.

[0085] Examples 29 - 33: Curable Composition The following examples show curable compositions containing the polyorganosiloxanes of the present invention.

[0086] Example 29. To a polypropylene mixing cup, 1.543 g of Example 17 and 1.020 g of an amine-functional siloxane (see Table 1) are added. Immediately, the mixture is placed in a rotary centrifuge mixer at 3000 revolutions per minute for 20 seconds. When the mixture is taken out of the mixer, it becomes warm and appears as a transparent, yellowish, non-flowing elastomeric gel. Example 29 shows a curable composition containing the polyorganosiloxane of the present invention (Example 17) that can rapidly crosslink an amine-functional siloxane polymer under ambient conditions. The gel sample is placed in a vacuum oven and dried at 80 °C under vacuum for 3 hours to remove the solvent. The resulting material is a transparent, non-sticky, yellowish elastomer having excellent mechanical toughness.

[0087] Example 30. To a polypropylene mixing cup, 2.189 g of Example 17 and 1.039 g of an amine-functional siloxane (see Table 1) are added. Immediately, the mixture is placed in a rotary centrifuge mixer at 3000 revolutions per minute for 20 seconds. When the mixture is taken out of the mixer, it becomes warm and appears as a transparent, yellowish, non-flowing elastomeric gel. Example 30 shows a curable composition containing the polyorganosiloxane of the present invention (Example 17) that can rapidly crosslink an amine-functional siloxane polymer under ambient conditions.

[0088] Example 31. To a polypropylene mixing cup, 0.584 g of Example 17 and 0.043 g of an epoxy-functional siloxane (see Table 1) are added. Immediately, the resulting mixture is placed in a rotary centrifuge mixer and subjected to a mixing cycle of 20 seconds at 3000 revolutions per minute for 2 times. The resulting mixture is a transparent, low-viscosity mixture and remains as such for about 24 hours. After 13 days at 25 °C and a relative humidity of about 50%, the sample becomes a hard, transparent, colorless and transparent elastomer without stickiness on the surface.

[0089] Example 32. 1.006 g of the dried polymer of Example 24 and 0.179 g of amine-functional siloxane 2 are added to a polypropylene mixing cup. Immediately, the mixture is placed in a rotary centrifugal mixer at 3000 revolutions per minute for 30 seconds. The mixture appears as a transparent, slightly crosslinked, non-flowing elastomeric gel with a yellowish tint that snaps back when probed and stretched with a spatula. After standing at room temperature for 9 days, the sample is a shiny-surfaced, lightly yellowish, low-tack, flexible, transparent elastomer that can be removed intact from the mixing cup.

[0090] Example 33. 1.004 g of the dried polymer of Example 24 and 0.466 g of amine-functional siloxane 2 are added to a polypropylene mixing cup. Immediately, the mixture is placed in a rotary centrifugal mixer at 3000 revolutions per minute for 30 seconds. The mixture appears as a transparent, faintly orange-tinted, non-flowing elastomeric gel with higher stiffness and lower elongation than the elastomer sample of Example 31. After standing at room temperature for 9 days, the sample is a lightly yellowish, low-tack, flexible, transparent elastomer that can be removed intact from the mixing cup.

Claims

Claim 1: A polyorganosiloxane having an anhydride functional group and an aromatic functional group, wherein the carbon of the aromatic functional group is separated from the carbon of the carbonyl group of the anhydride functional group by a carbon chain, and the polyorganosiloxane contains 5% by weight or more of silicon atoms based on the weight of the polyorganosiloxane. The anhydride functional group and the aromatic functional group are on the same pendant group extending from a single silicon atom of the polyorganosiloxane, and the aromatic functional group is further away from the silicon atom along the pendant portion than the anhydride functional group. A process for producing a polyorganosiloxane, the process comprising: (a) generating a reactive composition by combining (i) an unsaturated polyorganosiloxane, (ii) an unsaturated anhydride compound, (iii) a free radical initiator and / or a photoinitiator, and (iv) a solvent; and (b) initiating a free radical reaction by triggering the free radical initiator and / or the photoinitiator, wherein the solvent is an aromatic compound having an alpha hydrogen atom and / or the free radical initiator and / or the photoinitiator is aromatic. Claim 2 The process according to claim 1, wherein the unsaturated polyorganosiloxane is a vinyl-functional polyorganosiloxane. Claim 3 The process according to any one of claims 1 and 2, wherein the unsaturated anhydride compound is maleic anhydride or a substituted maleic anhydride. Claim 4 The process according to any one of claims 1 to 3, wherein the solvent is an aromatic solvent selected from one or more combinations of the group consisting of toluene, xylene isomers, ethylbenzene, and trimethylbenzene isomers. Claim 5 (a) A polyorganosiloxane having an anhydride functional group and an aromatic functional group, wherein the carbon of the aromatic functional group is separated from the carbon of the carbonyl group of the anhydride functional group by a carbon chain, and the polyorganosiloxane contains 5% by weight or more of silicon atoms based on the weight of the polyorganosiloxane. The anhydride functional group and the aromatic functional group are on the same pendant group extending from a single silicon atom of the polyorganosiloxane, and the aromatic functional group is further away from the silicon atom along the pendant portion than the anhydride functional group, a polyorganosiloxane, and (b) an organopolysiloxane containing on average at least two silicon-bonded amines or two silicon-bonded epoxy groups per molecule, a curable composition containing the same.

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