Silicone Polyoxamide Copolymer

Abstract

Silicone polyoxamides and silicone polyoxamide-hydrazide copolymers contain at least two repeating units of formula I, where each R 1 are independently alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently alkylene, aralkylene, or a combination thereof; each G is independently a bond or a group of formula R 3 HN-G-NHR 3 Diamine to two -NHR 3 is a divalent residue equivalent to the group R 3 are independently hydrogen or alkyl, or R 3 together with G and the nitrogen to which they are both attached form a heterocyclic group, each n is independently an integer from 0 to 300, each p is independently an integer from 1 to 25, the average of p is 1.3 or greater, and each q is independently an integer from 1 to 2, the average of q is 1.05 or less. JPEG2023507403000034.jpg24127

Description

[Background technology]

[0001] [Related Applications] This application is related to commonly assigned, copending provisional application No. 62 / 950,806, filed December 19, 2019, entitled "SILICONE POLYOXAMIDE COPOLYMERS WITH AMINE-BASED END GROUPS," the contents of which are incorporated in their entirety.

[0002] [Background technology] Siloxane polymers have unique properties that stem primarily from the physical and chemical characteristics of the siloxane bond. These properties include low glass transition temperatures, thermal and oxidative stability, resistance to ultraviolet light, low surface energy and hydrophobicity, high permeability to many gases, and biocompatibility. However, siloxane polymers often lack tensile strength.

[0003] The low tensile strength of siloxane polymers can be improved by forming block copolymers. Some block copolymers contain "soft" siloxane polymer blocks or segments and any of a variety of "hard" blocks or segments. Polydiorganosiloxane polyamides, polydiorganosiloxane polyureas, and polydiorganosiloxane polyoxamide copolymers are exemplary block copolymers.

[0004] Polydiorganosiloxane polyamides have been prepared by the condensation reaction of amino-terminated silicones with short-chain dicarboxylic acids. Alternatively, these copolymers have been prepared by the condensation reaction of carboxy-terminated silicones with short-chain diamines. Because polydiorganosiloxanes (e.g., polydimethylsiloxanes) and polyamides often have significantly different solubility parameters, it can be difficult to find reaction conditions for producing siloxane-based polyamides with high degrees of polymerization, especially those with larger homologs of polyorganosiloxane segments. Many known siloxane-based polyamide copolymers contain relatively short segments of polydiorganosiloxane (e.g., polydimethylsiloxane), e.g., segments with 30 or fewer diorganosiloxy (e.g., dimethylsiloxy) units, or the amount of polydiorganosiloxane segments in the copolymer is relatively low. That is, the proportion (ie, amount by weight) of polydiorganosiloxane (eg, polydimethylsiloxane) soft segments in the resulting copolymer tends to be low.

[0005] Polydiorganosiloxane polyoxamides, such as those disclosed in U.S. Patent No. 7,501,184 (Leir et al.), are yet another type of block copolymer. Known polydiorganosiloxane polyoxamide copolymers have been prepared by mixing a diamine, such as ethylenediamine, with a precursor having at least one polydiorganosiloxane segment and at least two oxalylamino groups. The resulting copolymer has alternating soft polydiorganosiloxane segments (S) and hard oxamide segments (H) (i.e., the copolymer is (SH)). n (These polydiorganosiloxane polyoxamide copolymers are of the polydiorganosiloxane type. Thus, these polydiorganosiloxane polyoxamide copolymers contain a relatively large proportion of polydiorganosiloxane segments compared to many known polydiorganosiloxane polyamide copolymers. Such polydiorganosiloxane polyoxamide copolymers can typically be exposed to high temperatures up to 250°C or higher without appreciable decomposition.

[0006] Further polydiorganosiloxane polyoxamide copolymers are described in U.S. Patent Nos. 7,981,995 and 8,124,713 (Hays et al.). Such polydiorganosiloxane polyoxamide copolymers are characterized by a more random distribution of hard segments (H) among the soft segments (S), with the extra "runs" of hard segments providing improved properties in the described applications.

[0007] In view of the above, the present inventors have recognized that while the alternating soft and hard segment polydiorganosiloxane polyoxamide copolymers described above represent an improvement over thermoplastic silicone elastomers, which have poor thermal stability, it would be advantageous to have the ability to reliably control the distribution of hard segments within the copolymer chain while speeding up or eliminating process steps that may be necessary to produce such copolymers. Furthermore, as described in applicant's co-pending application, Attorney Docket No. 82293US002, entitled "SILICONE POLYOXAMIDE COPOLYMERS WITH AMINE-BASED END GROUPS," the performance of the resulting copolymer in certain adhesive compositions can be enhanced by "capping" the intermediate structure with desired end groups, allowing for further application customization.

[0008] Briefly, in one aspect, the present disclosure provides a polymerizable composition comprising at least two repeat units of formula I: [ka] The present invention provides silicone polyoxamides and silicone polyoxamide-hydrazide copolymers comprising:

[0009] In this formula, each R 1are independently alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently alkylene, aralkylene, or a combination thereof; each G is independently a bond or a group of formula R 3 HN-G-NHR 3 Diamine to two -NHR 3 is a divalent residue equivalent to the group R 3 are independently hydrogen or alkyl, or R 3 together with G and the nitrogen to which they are both attached form a heterocyclic group, each n is independently an integer from 0 to 300, each p is independently an integer from 1 to 25, the average of p is 1.3 or greater, and each q is independently an integer from 1 to 2, the average of q is 1.05 or less.

[0010] Silicone polyoxamide and silicone polyoxamide-hydrazide copolymers have both hard and soft segments. The soft segments are provided by silicone-based amines with polydiorganosiloxane segments p. The hard segments are provided by oxamide group containing segments q.

[0011] In another aspect, the present disclosure provides a compound comprising at least two repeat units of formula I': [ka] [In the formula, R 1 , Y., G., R. 3 , n, p, and q are defined above.

[0012] The method comprises: (a) an oxalate ester of formula II [ka] [In the formula, each R 2are independently alkyl, haloalkyl, aryl, or alkyl, alkoxy, halo, alkyloxycarbonyl, or a substituted or unsubstituted alkyl group bonded via N. [ka] (In the formula, each R 4 are independently hydrogen, alkyl, or aryl, or R 4 (b) a polydiorganosiloxane diamine of Formula III; [ka] reacting until essentially no oxalate ester remains, Reaction product of formula IV [ka] and forming (c) one or more diamines of formula V [ka] to the reaction product of formula IV to form the repeat unit of formula I'; Includes.

[0013] Known methods for producing polydiorganosiloxane polyoxamide copolymers, such as those disclosed in U.S. Patent Nos. 7,501,184 (Leir et al.), 8,764,881, 7,981,985, and 8,124,713 (Hays et al.), can require costly excess oxalate, require recrystallization in certain processes, or can result in undesirable rheological properties for mounting and other adhesive applications. However, the methods of the present disclosure can be used to produce copolymers that are particularly suitable for use in pressure-sensitive adhesives and article mounting, and require fewer steps and fewer raw materials to produce the copolymers.

[0014] The present disclosure further provides an adhesive composition comprising the above-described silicone copolymer. The adhesive composition of the present disclosure may comprise a silicone polyoxamide copolymer or a silicone polyoxamide-hydrazide copolymer, a tackifying resin, and optionally a filler. The adhesive composition may be at least one of pressure-sensitive and heat-activated, as these terms are defined below. In some embodiments, the adhesive composition comprises at least one of a silicone polyoxamide or a silicone polyoxamide-hydrazide copolymer, a silicate tackifying resin, and optionally an inorganic particle filler. The adhesive composition may be stretch-releasable or peel-releasable, and may be damage-free. DETAILED DESCRIPTION OF THE INVENTION

[0015] The silicone polyoxamide and silicone polyoxamide-hydrazide copolymers of the present disclosure contain at least two repeat units of Formula I: [ka] Includes.

[0016] In this formula, each R 1 are independently alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently alkylene, aralkylene, or a combination thereof; each G is independently a bond or a group of formula R 3 HN-G-NHR 3 Diamine to two -NHR 3 is a divalent residue equivalent to the group R 3 are independently hydrogen or alkyl, or R 3 together with G and the nitrogen to which they are both attached form a heterocyclic group (e.g., R 3 HN-G-NHR 3is piperazine, etc.), each n is independently an integer of 0 to 300, each p is independently an integer of 1 to 25, the average of p is 1.3 or more, and each q is independently an integer of 1 to 2, the average of q is 1.05 or less.

[0017] R in Formula I 1 Suitable alkyl groups for R typically have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, and isobutyl. 1 Suitable haloalkyl groups for R often have only a portion of the hydrogen atoms of the corresponding alkyl group replaced with halogen. Exemplary haloalkyl groups include chloroalkyl and fluoroalkyl groups having 1 to 3 halo atoms and 3 to 10 carbon atoms. 1 Suitable alkenyl groups for R often have 2 to 10 carbon atoms. Exemplary alkenyl groups often have 2 to 8, 2 to 6, or 2 to 4 carbon atoms, such as ethenyl, n-propenyl, and n-butenyl. 1 Suitable aryl groups for often have 6 to 12 carbon atoms. Phenyl is an exemplary aryl group. The aryl group can be unsubstituted or substituted with alkyl (e.g., alkyl having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), alkoxy (e.g., alkoxy having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), or halo (e.g., chloro, bromo, or fluoro). R 1 Suitable aralkyl groups typically have an alkylene group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms. In some exemplary aralkyl groups, the aryl group is phenyl and the alkylene group has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms (i.e., the aralkyl structure is alkylene-phenyl, where the alkylene is attached to the phenyl group).

[0018] In some embodiments, in some repeat units of formula I, R 1 At least 40 percent, preferably at least 50 percent, of the groups are methyl. For example, R 1 At least 60 percent, at least 70 percent, at least 80 percent, at least 90 percent, at least 95 percent, at least 98 percent, or at least 99 percent of the groups may be methyl. 1 The groups may be selected from alkyl having at least 2 carbon atoms, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo.

[0019] Each Y in Formula I is independently alkylene, aralkylene, or a combination thereof. Suitable alkylene groups typically have up to 10 carbon atoms, up to 8 carbon atoms, up to 6 carbon atoms, or up to 4 carbon atoms. Exemplary alkylene groups include methylene, ethylene, propylene, and butylene. Suitable aralkylene groups typically have an arylene group having 6 to 12 carbon atoms bonded to an alkylene group having 1 to 10 carbon atoms. In some exemplary aralkylene groups, the arylene moiety is phenylene. That is, the divalent aralkylene group is a phenylene-alkylene, where the phenylene is bonded to an alkylene group having 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. As used herein, with respect to the Y group, "combinations thereof" refers to a combination of two or more groups selected from alkylene groups and aralkylene groups. For example, the combination can be a single aralkylene bonded to a single alkylene (e.g., alkylene-arylene-alkylene). In one exemplary alkylene-arylene-alkylene combination, the arylene is phenylene and each alkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

[0020] Each G in formula I is independently a bond or a group of formula R3 HN-G-NHR 3 Diamine compounds with two amino groups (i.e., -NHR 3 When G is a bond, the copolymer is a silicone polyoxamide-hydrazide. In some embodiments, G is a bond and each R 3 is hydrogen.

[0021] When G is a residue unit, the copolymer is a silicone polyoxamide. The diamine may have primary or secondary amino groups. 3 The group is hydrogen or alkyl (e.g., alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon atoms), or R 3 together with G and the nitrogen to which they are both attached form a heterocyclic group (e.g., R 3 HN-G-NHR 3 is piperazine). In most embodiments, R 3 is hydrogen or alkyl. In many embodiments, both of the amino groups in the diamine are primary amino groups (i.e., R 3 groups are both hydrogen), the diamine is a diamine of the formula H2N-G-NH2.

[0022] In some embodiments, G is alkylene, heteroalkylene, arylene, aralkylene, or a combination thereof. Suitable alkylenes often have 2 to 10, 2 to 6, or 2 to 4 carbon atoms. Exemplary alkylene groups include ethylene, propylene, butylene, and the like. Suitable heteroalkylenes are often polyoxyalkylenes, such as polyoxyethylene having at least two ethylene units, polyoxypropylene having at least two propylene units, or copolymers thereof. Suitable aralkylene groups typically contain an arylene group having 6 to 12 carbon atoms bonded to an alkylene group having 1 to 10 carbon atoms. Some exemplary aralkylene groups are phenylene-alkylenes, where the phenylene is bonded to an alkylene group having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. As used herein, with respect to the G group, "combinations thereof" refers to a combination of two or more groups selected from alkylene, heteroalkylene, arylene, and aralkylene. The combination may be, for example, an aralkylene bonded to an alkylene (e.g., alkylene-arylene-alkylene). In one exemplary alkylene-arylene-alkylene combination, the arylene is phenylene, and each alkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

[0023] Each subscript n in Formula I is independently an integer from 0 to 300. For example, subscript n can be an integer of at most 275, at most 250, at most 200, at most 100, at most 80, at most 60, at most 40, at most 20, or at most 10. The value of n is often at least 1, at least 2, at least 3, at least 5, at least 10, at least 20, or at least 40. For example, subscript n can be in the range of 40 to 300, 1 to 300, 1 to 200, 1 to 100, 1 to 80, 1 to 40, or 1 to 20.

[0024] Each subscript p is independently an integer from 1 to 25. For example, the value of p is often an integer at most 9, at most 8, at most 7, at most 6, at most 5, at most 4, at most 3, or at most 2. The value of p can be in the range of 1 to 8, 1 to 6, or 1 to 4. The average of p is 1.3 or greater.

[0025] The soft segments (p) tend to be present in the copolymers of Formula I with a multimodal distribution of number average molecular weights.

[0026] Each subscript q is independently an integer from 1 to 2, with substantially all qs being 1. In some embodiments, each subscript q is an integer equal to 1. The average q is 1.05 or less. Without wishing to be bound by theory, an average q of 1.05 or less limits the number of crosslinks in the hard segments, maintaining the copolymer of the present disclosure below the gel point. Use of such copolymers in adhesive compositions can result in at least one of increased shear strength and improved peel adhesion to the target adherend.

[0027] Failure to maintain q at an average of 1.05 or less can result in too many hard segment runs (i.e., q greater than or equal to 2), resulting in an adhesive composition that is overly stiff and undesirable for certain applications. Such compositions may be poorly tacky and / or may exhibit poor wetting on the surface. Adhesive compositions characterized by an average q greater than 1.05 may be particularly undesirable for application applications, as detailed below.

[0028] The values ​​of q and p can be controlled by the ratios of ingredients used to prepare the precursor of Formula IV below in producing the copolymer of Formula I'. A sufficient molar amount of amino groups in the polydiorganosiloxane diamine of Formula III (e.g., the amount necessary to achieve a molar ratio with the oxalate ester compound of Formula II of at least 0.56:1) tends to favor the formation of the precursor of Formula IV such that when carried forward to the copolymer of Formula I', a substantial majority of the compounds have q equal to 1 (i.e., q averages 1.05 or less). Furthermore, a molar ratio (i.e., stoichiometric ratio) of silicone amine to oxalate ester of at least 0.56:1 can help ensure p is 1.3 or greater.

[0029] The molar ratio of total amine to oxalate ester in the copolymer of formula I is typically about 0.96:1.04. The copolymers of the present disclosure are copolymers of formula -R a -(CO)-NH-[wherein, R a is alkylene]. All or nearly all of the carbonylamino groups along the backbone of the copolymer material are part of an oxalylamino group (i.e., a -(CO)-(CO)-NH- group). That is, every carbonyl group along the backbone of the copolymer material is bonded to another carbonyl group and becomes part of an oxalyl group. More specifically, the copolymers of the present disclosure have multiple aminooxalylamino groups.

[0030] The silicone polyoxamide and silicone polyoxamide-hydrazide copolymers of the present disclosure (and other silicone polyoxamide and silicone polyoxamide-hydrazide copolymers) can be prepared according to the method of the present disclosure by combining at least two repeating units of formula I' using the following method: [ka] [In the formula, each R 1are independently alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently alkylene, aralkylene, or a combination thereof; each G is independently a bond or a group of formula R 3 HN-G-NHR 3 Diamine to two -NHR 3 is a divalent residue equivalent to the group R 3 are independently hydrogen or alkyl, or R 3 together with G and the nitrogen to which they are both attached form a heterocyclic group, each n is independently an integer from 0 to 300, each p is independently an integer from 1 to 25, the average p is 1.3 or greater, and each q is independently an integer from 1 to 2, the average q is 1.05 or less.

[0031] R 1 , Y, G, and R 3 Suitable examples of are the same as those described above for Formula I.

[0032] The first step of the disclosed method is to prepare an oxalate ester of formula II [ka] [In the formula, each R 2 are independently alkyl, haloalkyl, aryl, or alkyl, alkoxy, halo, alkyloxycarbonyl, or a substituted or unsubstituted alkyl group bonded via N. [ka] (In the formula, each R 4 are independently hydrogen, alkyl, or aryl, or R 4 is an aryl substituted with (wherein, taken together, form a ring) to a solvent.

[0033] The two R groups in the oxalate of formula II 2The groups may be the same or different. In some methods, two R 2 The groups are different and have different reactivities with the polydiorganosiloxane diamines of formula III below.

[0034] R 2 Suitable alkyl and haloalkyl groups for often have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Tertiary alkyl groups (e.g., tert-butyl) and haloalkyl groups can be used, but often there is a primary or secondary carbon atom directly connected (i.e., bonded) to the adjacent oxy group. Exemplary alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. Exemplary haloalkyl groups include chloroalkyl and fluoroalkyl groups, in which some (but not all) of the hydrogen atoms on the corresponding alkyl group are replaced with halo atoms. For example, the chloroalkyl or fluoroalkyl group can be chloromethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3-chloropropyl, 4-chlorobutyl, fluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 4-fluorobutyl, and the like. R 2 Suitable aryl groups include those having 6 to 12 carbon atoms, such as phenyl. The aryl group can be unsubstituted or substituted with alkyl (e.g., alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, or n-propyl), alkoxy (e.g., alkoxy having 1 to 4 carbon atoms, such as methoxy, ethoxy, or propoxy), halo (e.g., chloro, bromo, or fluoro), or alkoxycarbonyl (e.g., alkoxycarbonyl having 2 to 5 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, or propoxycarbonyl).

[0035] The oxalate of formula II can be, for example, a compound of formula R 2It can be prepared by reacting an alcohol of -OH with oxalyl dichloride. Commercially available oxalates of Formula II (e.g., from Sigma-Aldrich (Milwaukee, WI) and VWR International (Bristol, CT)) include, but are not limited to, dimethyl oxalate, diethyl oxalate, di-n-butyl oxalate, di-tert-butyl oxalate, bis(phenyl) oxalate, bis(pentafluorophenyl) oxalate, 1-(2,6-difluorophenyl)-2-(2,3,4,5,6-pentachlorophenyl) oxalate, and bis(2,4,6-trichlorophenyl) oxalate.

[0036] Particularly useful oxalates of formula II include, for example, the oxalates of phenol, methyl ethyl ketone oxime, acetone oxime, and trifluoroethanol, the latter being particularly preferred at present.

[0037] Suitable solvents include, for example, tetrahydrofuran, methyl tert-butyl ether, toluene, ethyl acetate, dichloromethane, chloroform, and the like, or any solvent which does not interfere with the desired reaction.

[0038] Once the oxalate ester has been added to the solvent, or thereafter, the polydiorganosiloxane diamine of formula III is added and allowed to react with the oxalate ester. [ka]

[0039] The molar ratio of the oxalate ester of Formula II to the polydiorganosiloxane diamine of Formula III is generally controlled to at least about 1:0.56. A molar ratio of at least 1:0.56 can ensure that the oxalate ester of Formula II is completely consumed during the reaction under typical observations. As used herein, "completely consumed" and variations thereof mean that 5% or less of the oxalate ester initially added to the solvent remains available for reaction, as detected, for example, by gas chromatography. In other words, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or at least 99.5% of the oxalate ester initially added to the solvent is converted during the reaction. Without wishing to be bound by theory, complete consumption of the oxalate ester of Formula II helps to maintain q in Formula I as close to 1 as possible by limiting the binding sites available for the production of "continuous" hard segments (i.e., q is equal to 2).

[0040] The polydiorganosiloxane diamine of Formula III can be prepared by any known method and can have a suitable molecular weight, for example, a number average molecular weight ranging from 1,000 to 20,000 g / mol. In some currently preferred embodiments, the polydiorganosiloxane diamine of Formula III has a number average molecular weight of about 1,000 g / mol to about 15,000 g / mol, and in other currently preferred embodiments, the polydiorganosiloxane diamine of Formula III has a number average molecular weight of about 10,000 g / mol to about 15,000 g / mol. The inventors have discovered that starting with a polydiorganosiloxane diamine of Formula III having a number average molecular weight of less than 20,000 g / mol results in a relatively higher total number of hard segments in the copolymers of the present disclosure, compared to, for example, starting with a number average molecular weight of 25,000 g / mol or greater. Without wishing to be bound by theory, it is believed that an insufficient number of hard segments in the polymer, as is typically the case when starting with polydiorganosiloxane diamines of formula III having a number average molecular weight greater than about 23,000 g / mol, tends to reduce the shear holding strength and other performance properties of such adhesives.Furthermore, the resulting compositions are difficult to coat onto many desirable backings and other substrates. Suitable polydiorganosiloxane diamines and methods for producing them are described, for example, in U.S. Patent Nos. 3,890,269 (Martin), 4,661,577 (Jo Lane et al.), 5,026,890 (Webb et al.), 5,276,122 (Aoki et al.), 5,214,119 (Leir et al.), 5,461,134 (Leir et al.), 5,512,650 (Leir et al.), and 6,355,759 (Sherman et al.). Some polydiorganosiloxane diamines are commercially available, for example, from Gelest Inc. (Morrisville, PA).

[0041] Polydiorganosiloxane diamines having molecular weights greater than 5,000 g / mole can be prepared using the methods described in U.S. Patent Nos. 5,214,119 (Leir et al.), 5,461,134 (Leir et al.), and 5,512,650 (Leir et al.). One of the methods described comprises reacting, under reactive conditions and an inert atmosphere, (a) an amine-functional endblocking agent of the formula: [ka] [Wherein, Y and R 1 is the same as defined for Formula I'; (b) sufficient cyclic siloxane to react with an amine functional endblocker to form a polydiorganosiloxane diamine having a molecular weight of less than 2,000 g / mole; and (c) an anhydrous aminoalkylsilanolate catalyst of the formula: [ka] [Wherein, Y and R 1 is the same as defined in formula I', M + is sodium ion, potassium ion, cesium ion, rubidium ion, or tetramethylammonium ion. The reaction continues until substantially all of the amine-functional endblocking agent is consumed, after which additional cyclic siloxane is added to increase molecular weight. The additional cyclic siloxane is often added slowly (e.g., dropwise). The reaction temperature is often in the range of 80°C to 90°C, and the reaction time is 5 to 7 hours. The resulting polydiorganosiloxane diamine can be highly pure (e.g., silanol impurities less than 2 weight percent, less than 1.5 weight percent, less than 1 weight percent, less than 0.5 weight percent, less than 0.1 weight percent, less than 0.05 weight percent, or less than 0.01 weight percent). The molecular weight of the resulting polydiorganosiloxane diamine of Formula III can be varied by varying the ratio of amine-endfunctional blocking agent to cyclic siloxane.

[0042] Another method for preparing the polydiorganosiloxane diamine of Formula III is to combine, under reactive conditions and in an inert environment, (a) an amine functional endblocker of the following formula: [ka] [In the formula, R 1 and Y are the same as those described for Formula I', and the subscript x is equal to an integer between 1 and 150; (b) sufficient cyclic siloxane to provide a polydiorganosiloxane diamine having an average molecular weight greater than that of the amine-functional endblocker; and (c) a catalyst selected from cesium hydroxide, cesium silanolate, rubidium silanolate, cesium polysiloxanolate, rubidium polysiloxanolate, and mixtures thereof. The reaction is continued until substantially all of the amine-functional endblocker is consumed. This method is further described in U.S. Patent No. 6,355,759 (B1) (Sherman et al.). Using this procedure, polydiorganosiloxane diamines of any molecular weight can be prepared.

[0043] Yet another method for preparing polydiorganosiloxane diamines of Formula III is described in U.S. Patent No. 6,531,620 B2 (Brader et al.) in which a cyclic silazane is reacted with a siloxane material having hydroxy end groups, as shown in the following reaction: [ka]

[0044] R 1 The groups , and Y are the same as those described for formula I'. The subscript m is an integer greater than 1.

[0045] Examples of polydiorganosiloxane diamines include, but are not limited to, polydimethylsiloxane diamine, polydiphenylsiloxane diamine, polytrifluoropropylmethylsiloxane diamine, polyphenylmethylsiloxane diamine, polydiethylsiloxane diamine, polydivinylsiloxane diamine, polyvinylmethylsiloxane diamine, poly(5-hexenyl)methylsiloxane diamine, and mixtures thereof.

[0046] The mixture of oxalate ester and polydiorganosiloxane diamine is reacted until essentially no polydiorganosiloxane diamine or oxalate ester remains, as determined (e.g., by gas chromatography), resulting in the formation of the precursor of Formula IV as the reaction product. [ka]

[0047] The resulting reaction mixture contains some ester-capped polydiorganosiloxane diamine, where p depends on the amount of oxalate ester used and the nature of the solvent used. The reaction mixture typically contains no more than trace amounts (i.e., less than 5% of the initial amount) of unreacted oxalate ester of Formula II, as determined (e.g., by gas chromatography).

[0048] One or more diamines of formula V are then added to the reaction product of formula IV to form the repeat unit of formula I'. [ka]

[0049] The diamine is typically added in an amount necessary to consume nearly all, if not all, of the remaining ester groups. This reaction is typically carried out in the presence of a catalyst, although the reaction can also be carried out in the absence of a catalyst. Suitable catalysts include protic acid catalysts such as acetic acid.

[0050] The molar ratio of the polydiorganosiloxane diamine of Formula III to the diamine of Formula V (i.e., the amine molar ratio) is often about 1:0.8 or less. The amine molar ratio is selected so that the molar ratio of total amine to ester in the copolymer of Formula I' is about 1.0:1.0 (i.e., 0.96:1 to 1:1.04). For example, the amine molar ratio can range from 1:0.4 to 1:0.75, from 1:0.45 to 1:0.7, or from 1:0.5 to 1:0.65. For example, varying the amine molar ratio can be used to change the overall molecular weight and the number of "runs" of hard segments, which can affect the rheology of the resulting copolymer. Furthermore, the molar ratio can be varied to provide oxalylamino-containing end groups or amino end groups, depending on which reactant is present in molar excess.

[0051] The diamine of Formula V may be classified as an organic diamine. Examples of organic diamines include those selected from alkylenediamines, heteroalkylenediamines, arylenediamines, aralkylenediamines, and alkylene-aralkylenediamines. Because the diamine contains only two amino groups, the resulting polydiorganosiloxane polyoxamides and polyoxamide-hydrazides are linear block copolymers that are often elastomeric, melt at high temperatures, and are soluble in several common solvents. The diamine does not include polyamines with three or more primary or secondary amino groups. Tertiary amines may be present that do not react with the reaction product of Formula IV. Furthermore, in certain embodiments, the diamine may not contain any carbonyl amino groups, i.e., the diamine is not an amide.

[0052] Exemplary polyoxyalkylene diamines (i.e., G is a heteroalkylene where the heteroatom is oxygen) include, but are not limited to, those commercially available from Huntsman (The Woodlands, TX) under the tradenames JEFFAMINE D-230 (i.e., a polyoxypropylene diamine having an average molecular weight of 230 g / mole), JEFFAMINE D-400 (i.e., a polyoxypropylene diamine having an average molecular weight of 400 g / mole), JEFFAMINE D-2000 (i.e., a polyoxypropylene diamine having an average molecular weight of 2,000 g / mole), JEFFAMINE HK-511 (i.e., a polyether diamine comprising both oxyethylene and oxypropylene groups and having an average molecular weight of 220 g / mole), JEFFAMINE ED-2003 (i.e., a polyethylene glycol capped with polypropylene oxide having an average molecular weight of 2,000 g / mole), and JEFFAMINE EDR-148 (i.e., a triethylene glycol diamine).

[0053] Exemplary alkylenediamines (i.e., G is alkylene) include, but are not limited to, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, 2-methylpentamethylene-1,5-diamine (i.e., commercially available from DuPont, Wilmington, Del., under the trade name DYTEK A), 1,3-pentanediamine (commercially available from DuPont under the trade name DYTEK EP), 1,4-cyclohexanediamine, 1,2-cyclohexanediamine (commercially available from DuPont under the trade name DHC-99), 4,4′-bis(aminocyclohexyl)methane, and 3-aminomethyl-3,5,5-trimethylcyclohexylamine.

[0054] Exemplary arylene diamines (i.e., G is an arylene such as phenylene) include, but are not limited to, m-phenylenediamine, o-phenylenediamine, and p-phenylenediamine. Exemplary aralkylene diamines (i.e., G is an aralkylene such as alkylene-phenyl) include, but are not limited to, 4-aminomethyl-phenylamine, 3-aminomethyl-phenylamine, and 2-aminomethyl-phenylamine. Exemplary alkylene-aralkylene diamines (i.e., G is an alkylene-aralkylene such as alkylene-phenylene-alkylene) include, but are not limited to, 4-aminomethyl-benzylamine, 3-aminomethyl-benzylamine, and 2-aminomethyl-benzylamine.

[0055] Exemplary hydrazines (ie, G is a bond) include, but are not limited to, hydrazine and N,N'-diaminopiperazine.

[0056] In some preferred embodiments, the diamine of Formula V is selected from the group consisting of 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-pentanediamine, 1,6-diaminohexane, and m-xylylenediamine.

[0057] Any suitable reactor (e.g., a glass vessel or standard kettle equipped with an agitator) or process can be used to prepare copolymer materials according to the methods of the present disclosure. The reaction can be carried out using a batch process, a semi-batch process, or a continuous process. An exemplary batch process can be carried out in a reaction vessel equipped with a mechanical agitator, such as a Brabender mixer, provided that the reaction product is in a molten state and has a low enough viscosity to be removed from the reactor. An exemplary semi-batch process can be carried out in a continuously stirred tube, tank, or fluidized bed. An exemplary continuous process can be carried out in a single-screw or twin-screw extruder, such as a wiped-surface counter-rotating or co-rotating twin-screw extruder.

[0058] The silicone polyoxamide and silicone polyoxamide-hydrazide copolymers of the present disclosure are linear block copolymers (i.e., containing hard and soft blocks) and can be elastomers. The silicone polyoxamide and silicone polyoxamide-hydrazide copolymers can be formulated to contain at least 93 weight percent polydiorganosiloxane segments (i.e., soft segments) based on the weight of the copolymer. In other embodiments, the silicone polyoxamide copolymers can be formulated to contain at least 94 weight percent, at least 95 weight percent, at least 96 weight percent, at least 97 weight percent, at least 98 weight percent, at least 99 weight percent, or at least 99.2 weight percent polydiorganosiloxane segments (i.e., soft segments) based on the weight of the copolymer. The weight percent of diorganosiloxane in the polydiorganosiloxane segments can be controlled by using a relatively low molecular weight polydiorganosiloxane of Formula III.

[0059] The copolymers of the present disclosure also tend to have improved thermal stability. Some of the copolymers of the present disclosure do not flow, for example, at temperatures below about 220° C., below about 260° C., or even below about 300° C. For purposes of this disclosure, the temperature at which a copolymer flows is defined as the temperature at which the copolymer becomes soft enough to be compressed to a thickness of 2 mm in an ARES parallel plate rheometer (available from TA Instruments, New Castle, Del.).

[0060] The copolymers of the present disclosure can be optically transparent. As used herein, the term "optically transparent" refers to a material that appears transparent to the human eye. Optically transparent copolymer materials often have a luminous transmittance of at least 90 percent, a haze of less than 2 percent, and an opacity of less than 1 percent in the wavelength range of 400 nm to 700 nm. Both the luminous transmittance and haze can be determined, for example, using the method of ASTM-D 1003-95.

[0061] Additionally, copolymers can have a low refractive index. As used herein, the term "refractive index" refers to the absolute refractive index of a material (e.g., a copolymer material), which is the ratio of the electromagnetic radiation velocity in free space to the electromagnetic radiation velocity in the material. Electromagnetic radiation is white light. The refractive index is measured using, for example, an Abbe refractometer available from Fisher Instruments (Pittsburgh, PA). Refractive index measurements can vary, to some extent, depending on the specific refractometer used. Copolymer materials typically have a refractive index in the range of 1.41 to 1.50.

[0062] The copolymers of the present disclosure can be cast from a solvent or cast and polymerized as a film, molded or embossed into various shapes, or extruded into a film. The high thermal stability of the copolymer material makes it well suited for film formation by extrusion methods. The film can be optically transparent. Multilayer films containing polydiorganosiloxane polyoxamide block copolymers are described, for example, in U.S. Patent No. 7,820,297 (Benson et al.).

[0063] The copolymers of the present disclosure are useful in a variety of articles. Examples of such articles include layers comprising the copolymers of the present disclosure and one or more optional substrates. For example, the copolymers of the present disclosure can be in a layer adjacent to a first substrate or disposed between a first substrate and a second substrate. That is, the article can be configured in the following order: a first substrate, a layer comprising the copolymers of the present disclosure, and a second substrate. As used herein, the term "adjacent" refers to a first layer that is in contact with a second layer or that is disposed near the second layer but is separated from the second layer by one or more additional layers.

[0064] The copolymers of the present disclosure are also useful as low adhesion backsize coatings.

[0065] Adhesive compositions featuring silicone polyoxamide copolymers The silicone polyoxamide copolymers of the present disclosure can be incorporated into adhesive compositions such as pressure-sensitive adhesives containing tackifiers and heat-activated adhesives. Such adhesive compositions are further described, for example, in U.S. Pat. No. 7,371,464 (Sherman et al.) and U.S. Pat. No. 8,691,391 (Sherman et al.). The copolymers of the present disclosure can be incorporated into both stretch-release and peel-release compositions. In embodiments featuring stretch-releasable adhesives, the article can be removed from a substrate or surface by stretching at an angle of less than 35°. In embodiments featuring peel-releasable (i.e., releasable) adhesives, the article is a single-layer or multi-layer structure that can be removed from a substrate or surface by stretching at an angle of 35° or greater. In some embodiments, the releasable adhesive can be removed by a combination of stretch-release and peel-release mechanisms.

[0066] Furthermore, the copolymers of the present disclosure can be used as hot melt adhesives. Typically, hot melt adhesives contain little or no tackifier. Hot melt adhesives can be used, for example, to bond two surfaces together to form a composite. That is, hot melt adhesives can be used to bond a first substrate to a second substrate with the hot melt adhesive disposed between the first and second substrates. When applied to a surface, such as a substrate surface, it is desirable for the hot melt adhesive to be sufficiently fluid to completely wet the surface and avoid voids, even if the surface is rough. Such adhesive compositions typically have a low viscosity upon application and then solidify upon cooling. Cohesive strength is developed upon cooling. Alternatively, the hot melt adhesive composition can be formulated with a solvent or carrier that reduces the viscosity sufficiently to wet the surface. The solvent or carrier can then be removed to provide a solid coating with cohesive strength.

[0067] Tackifiers, plasticizers, and other property modifiers may be incorporated into adhesive compositions containing the copolymers of the present disclosure. Preferred optional additives are not hot-melt processable, i.e., they do not melt and flow at temperatures at which the copolymers of the present disclosure melt and flow.

[0068] Tackifying materials or plasticizers useful for polymeric materials are preferably miscible at the molecular level, e.g., soluble in any or all polymer segments of elastomeric or thermoplastic elastomer materials. Examples of tackifying agents suitable for the present disclosure include, but are not limited to, silicone fluids, liquid rubbers, hydrocarbon resins, rosins, natural resins such as dimerized or hydrogenated balsams and esterified abietic acid, polyterpenes, terpene phenolic resins, phenol-formaldehyde resins, and rosin esters. Examples of plasticizers include, but are not limited to, polybutenes, paraffinic oils, petrolatum, and certain phthalates with long aliphatic side chains, such as ditridecyl phthalate.

[0069] Other suitable tackifiers include silicate tackifying resins. Suitable silicate tackifying resins include those having the following structural unit M (i.e., monovalent RSiO 1 / 2 units), D (i.e., divalent R2SiO 2 / 2 units), T (i.e., trivalent RSiO 3 / 2 units), and Q (i.e., tetravalent SiO 4 / 2 units), and resins composed of combinations thereof. Typical exemplary silicate resins include MQ silicate tackifying resins, MQD silicate tackifying resins, and MQT silicate tackifying resins. These silicate tackifying resins typically have number average molecular weights in the range of 100 to 50,000, or 500 to 15,000, and generally have methyl R groups.

[0070] MQ silicate tackifying resin is R3SiO 1 / 2 Units ("M" units) and SiO 4 / 2units ("Q" units), where M units are bonded to Q units, each of which is bonded to at least one other Q unit. 4 / 2 The unit ("Q" unit) is attached to the hydroxyl group to form HOSiO 3 / 2 Some result in units ("TOH" units) that correspond to the silicon-bonded hydroxyl content of the silicate tackifying resin, while others result in SiO 4 / 2 Some are only attached to units.

[0071] Such resins are described, for example, in Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley & Sons, New York, (1989), pp. 265-270, as well as U.S. Pat. Nos. 2,676,182 (Daudt et al.), 3,627,851 (Brady), 3,772,247 (Flannigan), and 5,248,739 (Schmidt et al.). Other examples are disclosed in U.S. Pat. No. 5,082,706 (Tangney). The above resins are generally prepared in a solvent. Dry or solvent-free M silicone tackifying resins can be prepared as described in U.S. Pat. Nos. 5,319,040 (Wengrovius et al.), 5,302,685 (Tsumura et al.), and 4,935,484 (Wolfgruber et al.).

[0072] Certain MQ silicate tackifying resins can be prepared by the silica hydrosol capping process described in U.S. Patent No. 2,676,182 (Daudt et al.) and modified by U.S. Patent Nos. 3,627,851 (Brady) and 3,772,247 (Flannigan). These modified processes often involve limiting the concentration of the sodium silicate solution, and / or the ratio of silicon to sodium in the sodium silicate, and / or the time before capping the neutralized sodium silicate solution to values ​​generally lower than those disclosed by Daudt et al. Neutralized silica hydrosols are often stabilized with an alcohol, such as 2-propanol, to form RSiO 1 / 2 The siloxane units are capped as soon as possible after neutralization. The silicon-bonded hydroxyl group (i.e., silanol) content on the MQ resin can be reduced to 1.5 weight percent or less, 1.2 weight percent or less, 1.0 weight percent or less, or 0.8 weight percent or less, based on the weight of the silicate tackifying resin. This can be done, for example, by reacting hexamethyldisilazane with the silicate tackifying resin. Such reactions can be catalyzed, for example, by trifluoroacetic acid. Alternatively, trimethylchlorosilane or trimethylsilylacetamide can be reacted with the silicate tackifying resin, in which case no catalyst is required.

[0073] MQD silicone tackifying resins can be prepared from, for example, RSiO as taught in U.S. Pat. No. 2,736,721 (Dexter). 1 / 2 Units ("M" units), SiO 4 / 2 units ("Q" units), and R2SiO 2 / 2 MQD silicone tackifying resins are terpolymers containing RSiO units ("D" units). 2 / 2 Some of the methyl R groups of the units (“D” units) may be replaced with vinyl (CH2=CH-) groups (“DVi” units).

[0074] MQT silicate tackifying resins are, for example, RSiO 2 as taught in U.S. Pat. No. 5,110,890 (Butler) and Japanese Patent Application Laid-Open No. 2-36234. 1 / 2 Units, SiO 4 / 2 Units, and RSiO 3 / 2 It is a terpolymer having units ("T" units).

[0075] Suitable silicate tackifying resins are commercially available from suppliers such as Dow Corning (Midland, MI), Momentive Performance Materials (Albany, NY), and Rhodia Silicones (Rock Hill, SC). Examples of particularly useful MQ silicate tackifying resins include those available under the tradenames SR-545 and SR-1000, both of which are commercially available from Momentive Performance Materials (Albany, NY). Such resins are generally supplied in organic solvents and may be used as received in the formulation of adhesives of the present disclosure. Blends of two or more silicate resins may be included in the adhesive composition.

[0076] Either pressure-sensitive or heat-activatable adhesives can be formulated by combining silicone polyoxamides and / or silicone polyoxamide-hydrazide copolymers and silicate tackifying resins with inorganic particles or other fillers. The inorganic particles included in the adhesive composition tend to improve the performance of the resulting adhesive. More specifically, inorganic particles tend to increase the cohesive strength and rubbery plateau modulus of the pressure-sensitive adhesive. The inorganic particles can be uniformly or non-uniformly dispersed throughout the pressure-sensitive adhesive composition. The inorganic particles can be any suitable metal, metal alloy, metal oxide, ceramic material, or mixtures thereof. The inorganic particles are often selected from, but not limited to, alumina, titania, zirconia, silica, and the like.

[0077] In many embodiments, the inorganic particles are fumed silica particles. Suitable fumed silicas are commercially available, for example, from Evonik Industries (Essen, Germany) under the trade name AEROSIL (e.g., AEROSIL R972, R974, R976, R300, R380, R130, R150, R200, R202, R805, and R812) or from Cabot (Alpharetta, GA) under the trade name CABOSIL (e.g., CABOSIL TS-720, TS-610, TS-530, and TS-500). The fumed silica can have any suitable surface area. For example, the surface area can be from 1 to 500 m. 2 / g range, 10-400m 2 / g range or 100-400m 2 The fumed silica may have any suitable particle size. In some applications, the fumed silica has an average primary particle size of less than 30 microns, less than 15 microns, less than 10 microns, less than 5 microns, and less than 1 micron. Although nanoscale fumed silica can be used in certain implementations, the use of fumed silica with an average primary particle size of less than 200 nanometers may cause damage to the substrate. Although hydrophobic or hydrophilic fumed silica can be used, hydrophobic fumed silica is often used because the particles tend to disperse better in the organic solvents typically contained in various compositions.

[0078] In other embodiments, the inorganic particles are aerogels, such as silica aerogel particles (e.g., crushed aerogel or aerogel powder). Silica aerogel particles often have pores in the nanometer range (e.g., less than 100 nanometers or less than 50 nanometers) and are at least 500 nm in diameter. 2%. Exemplary silica aerogel particles can have an average particle size of less than 20 microns or less than 10 microns. Although the size of silica aerogel particles is larger than the wavelength of light, the particles are often translucent and can be used to form adhesive layers that are relatively transparent, even if not considered optically transparent. Exemplary silica aerogel particles in translucent and opaque grades are commercially available from Cabot (Billerica, MA) under the trade name NANOGEL.

[0079] Inorganic particles can be surface-modified to facilitate dispersion in silicone polymer or adhesive compositions, but they are often not surface-modified. The inorganic particles can be agglomerated or non-agglomerated, aggregated or non-aggregated. The inorganic particles can have any desired particle size or shape. When an optically transparent adhesive article is desired, the inorganic particles are often selected to have an average particle size of less than 1,000 nanometers. For example, the average particle size is often less than 500 nanometers, less than 200 nanometers, less than 100 nanometers, or less than 50 nanometers. Larger inorganic particles can be used to prepare adhesive articles that do not need to be optically transparent. For example, the inorganic particles can have an average particle size of up to 5 micrometers, up to 10 micrometers, up to 20 micrometers, up to 50 micrometers, or up to 100 micrometers.

[0080] The adhesive composition may optionally contain other additives to provide desired properties. For example, dyes and pigments may be added as colorants, conductive and / or thermally conductive compounds may be added to make the adhesive electrically and / or thermally conductive or antistatic, antioxidants and antibacterial agents may be added, and UV stabilizers and absorbers, such as hindered amine light stabilizers (HALS), may be added to stabilize the adhesive against UV degradation and block certain UV wavelengths from penetrating the article. Other additives include, but are not limited to, adhesion promoters, additional fillers (e.g., carbon fiber, carbon black, glass beads, glass and ceramic bubbles, glass fiber, mineral fiber, clay particles, organic fibers such as nylon, metal particles, or unexpanded polymer microspheres), tack enhancers, blowing agents, hydrocarbon plasticizers, and flame retardants.

[0081] The copolymers of the present disclosure are typically present in the adhesive composition in an amount of at least 20 wt % and no more than 80 wt %, based on the total weight of the adhesive composition, or any amount within that range. In certain implementations, it may be preferred for the copolymer to be present in a concentration of at least 30 wt % and no more than 75 wt %, based on the total weight of the adhesive composition.

[0082] The tackifier is typically added to the composition in an amount of at least 10 wt%, in some embodiments at least 30 wt%, in some embodiments at least 40 wt%, and in some embodiments at least 50 wt%, based on the total weight of the adhesive composition. The tackifier is typically present in the composition in an amount of no more than 70 wt%, no more than 65 wt%, and in some embodiments no more than 60 wt%, based on the total weight of the adhesive composition. In typical adhesive compositions for use in application applications herein, the tackifier is present in the composition in an amount of no more than about 60 wt% and no less than 40 wt%. Without wishing to be bound by theory, a tackifier concentration greater than about 60 wt% means that, under certain conditions, the tackifier will take on the continuous phase of the composition in favor of the copolymer. Adhesive compositions having a tackifier that forms a continuous phase tend to exhibit at least one of poor tack, poor adhesion, poor shear holding strength, and poor damage-free removal.

[0083] Typically, when used as a filler, inorganic particles are added at a concentration of about 0.1% to about 20% by weight, based on the total weight of the adhesive composition, or any amount within that range. In a currently preferred implementation, the inorganic particles are added in an amount of about 3% to about 15% by weight, more preferably about 5% to about 12% by weight, based on the total weight of the adhesive composition.

[0084] adhesive article Adhesive articles typically include a substrate and an adhesive layer adjacent to at least one surface of the substrate. Other adhesive articles of the present disclosure may not include a backing or substrate. Backing-free adhesive structures are described, for example, in U.S. Patent Application Publication No. 2016 / 0068722 (Schmitz-Stapela et al.). The adhesive layer includes an adhesive composition including a copolymer described herein. The substrate may include a single layer of material or a combination of two or more materials.

[0085] The substrate can have any useful form, including, but not limited to, a film, a sheet, a membrane, a filter, a nonwoven or woven fiber, a hollow or solid bead, a bottle, a plate, a tube, a rod, a pipe, or a wafer. The substrate can be porous or non-porous, rigid or flexible, transparent or opaque, colorless or colored, and reflective or non-reflective. The substrate can have a flat or relatively flat surface, or it can have texture, such as wells, indentations, channels, bumps, etc. The substrate can have a single layer or multiple layers of material. Suitable substrate materials include, for example, polymeric materials, glass, ceramics, sapphire, metals, metal oxides, hydrated metal oxides, or combinations thereof.

[0086] Suitable polymer substrate materials include, but are not limited to, polyolefins (e.g., polyethylenes such as biaxially oriented polyethylene or high-density polyethylene and polypropylenes such as biaxially oriented polypropylene), polystyrene, polyacrylates, polymethacrylates, polyacrylonitriles, polyvinyl acetates, polyvinyl alcohols, polyvinyl chloride, polyoxymethylene, polyesters such as polyethylene terephthalate (PET), polytetrafluoroethylene, ethylene-vinyl acetate copolymers, polycarbonates, polyamides, rayon, polyimides, polyurethanes, phenolic resins, polyamines, amino-epoxy resins, polyesters, silicones, cellulosic polymers, polysaccharides, nylon, neoprene rubber, or combinations thereof. Some polymeric materials are foams, woven fibers, nonwoven fibers, or films.

[0087] Suitable glass and ceramic substrate materials can include, for example, silicon, aluminum, lead, boron, phosphorus, zirconium, magnesium, calcium, arsenic, gallium, titanium, copper, or combinations thereof. Glasses typically include various types of silicate-containing materials.

[0088] Some substrates are release liners. The adhesive layer is applied to the release liner and then transferred to another substrate, such as a backing film or a foam substrate. Suitable release liners typically contain polymers such as polyester or polyolefin, or coated paper. Some adhesive articles are transfer tapes that include an adhesive layer positioned between two release liners. Exemplary release liners include, but are not limited to, fluorosilicone-coated polyethylene terephthalate, such as that disclosed in U.S. Pat. No. 5,082,706 (Tangney) and commercially available from Loparex, Inc., Bedford Park, IL. The liner can have a microstructure on its surface, which is applied to the adhesive to form a microstructure on the surface of the adhesive layer. The liner can be removed to obtain an adhesive layer with a microstructured surface.

[0089] In some embodiments, the adhesive article is a single-sided adhesive tape in which an adhesive layer is on a single major surface of a substrate, such as a foam or film. In other embodiments, the adhesive article is a double-sided adhesive tape in which an adhesive layer is on two major surfaces of a substrate, such as a foam or film. The two adhesive layers of the double-sided adhesive tape can be the same or different. For example, one adhesive can be a pressure-sensitive adhesive and the other a heat-activated adhesive, where at least one of the adhesives is based on the copolymer described in the present invention. Each exposed adhesive layer can be applied to a different substrate.

[0090] The adhesive article can contain additional layers, such as primers, barrier coatings, metallic and / or reflective layers, tie layers, and combinations thereof, which can be disposed between the substrate and the adhesive layer, adjacent to the substrate on the side opposite the adhesive layer, or adjacent to the adhesive layer on the side opposite the substrate.

[0091] In some embodiments, the adhesive article can further include a separable connector. Some exemplary separable connectors are described in, for example, U.S. Patent Nos. 6,572,945, 7,781,056, 6,403,206, and 6,972,141.

[0092] Some adhesive articles of the present disclosure have excellent shear strength. Some embodiments of the present disclosure have a shear strength of greater than 1800 minutes when measured by ASTM D3654-82, modified according to the following static shear test method. Some embodiments of the present disclosure have a shear strength of greater than 10,000 minutes when measured by modified ASTM D3654-82. Some embodiments of the present disclosure have a shear strength of greater than 50,000 minutes when measured by modified ASTM D3654-82.

[0093] Some adhesives that can be used in the adhesive articles of the present disclosure have a glass transition temperature, as determined by dynamic mechanical analysis of the tan δ peak value, of about −125° C. to 15° C. Some adhesives that can be used in the adhesive articles of the present disclosure have a storage modulus at 25° C. of about 400,000 Pa or less, or 300,000 Pa or less, as determined by dynamic mechanical analysis.

[0094] In some embodiments, the thickness of the adhesive on at least one of the first or second major surfaces of the multi-layer carrier is from about 1 μm to about 1 mm.

[0095] Some adhesive articles of the present disclosure have an elongation to break of greater than 50% in at least one direction. Some adhesive articles of the present disclosure have an elongation to break of from about 50% to about 1200% in at least one direction.

[0096] Some adhesive articles of the present disclosure have a tensile break strength that is high enough so that the adhesive article does not tear before being removed from the substrate at an angle of 35° or less.

[0097] Some adhesive articles of the present disclosure have a lower peel force (e.g., about 25 oz / in to about 50 oz / in) to make the adhesive article easier to remove. Some adhesive articles of the present disclosure can have a higher peel force (e.g., about 50 oz / in to about 100 oz / in) to allow the user to handle the adhesive article without accidental separation. Some embodiments of the present disclosure have a peel force of about 20 oz / in to about 90 oz / in. Some embodiments of the present disclosure have a peel force of about 30 oz / in to about 70 oz / in.

[0098] Some adhesive articles of the present disclosure have a tensile break strength that is high enough so that the adhesive article does not tear before being removed from the substrate at an angle of 35° or greater.

[0099] Some adhesive articles of the present disclosure can be removed from a substrate, wall, or surface (collectively, the adherend) without damage. As used herein, terms such as "without damage" and "without damage" mean that the adhesive article can be separated from the substrate without causing visible damage to the paint, coating, resin, covering, or underlying substrate and / or leaving behind any residue. Visible damage to the substrate can be, for example, in the form of scratches, tears, delamination, breaks, crumbles, distortions, blistering, bubbles, etc. of any layer of the substrate. Visible damage can also be discoloration, weakening, gloss change, haze change, or other changes in the appearance of the substrate.

[0100] Methods for making adhesive articles typically include providing a substrate and applying an adhesive composition to at least one surface of the substrate. The adhesive composition can be applied to the substrate by a wide range of processes, including, for example, solution coating, solution spraying, hot melt coating, extrusion, coextrusion, lamination, and pattern coating. The adhesive composition is often applied to the substrate at a density of 0.02 grams per 154.8 cm. 2 ~2.4g / 154.8cm 2 is applied to the surface of the substrate as an adhesive layer at a coating weight of 0.15 wt.

[0101] The adhesive articles of the present disclosure may be subjected to post-processing steps such as curing, crosslinking, die cutting, heating to cause expansion of the article, eg, foam-in-place.

[0102] Adhesive articles featuring the adhesive composition of the present disclosure can be used in a variety of ways. In some embodiments, the adhesive article is applied, attached, or pressed onto an adherend. In this way, the adhesive article comes into contact with the adherend. If a release liner is present, the release liner is removed before the adhesive article is applied, attached, or pressed onto the adherend. In some embodiments, at least a portion of the adherend is wiped with alcohol before the adhesive article is applied, attached, or pressed onto the adherend.

[0103] The adhesive article can be used in wet or humid environments, such as those found in bathrooms. For example, the adhesive article can adhere to toilets (e.g., toilet tanks), bathtubs, sinks, and walls. The adhesive article can also be used in showers, locker rooms, steam rooms, swimming pools, hot tubs, and kitchens (e.g., kitchen sinks, dishwashers, and backsplash areas, refrigerators, and coolers). The adhesive article can also be used in outdoor applications and low-temperature applications such as refrigerators. Useful outdoor applications include attaching articles such as signs to outdoor surfaces such as windows, doors, and vehicles.

[0104] The adhesive article (i.e., adhesive tape or in a single article) can be provided in any useful form, such as, for example, a tape, a strip, a sheet (e.g., a perforated sheet), a label, a roll, a web, a disc, and a kit (e.g., an object for attachment and the adhesive tape used to attach the object). Similarly, multiple adhesive articles can be provided in any suitable form, including, for example, a tape, a strip, a sheet (e.g., a perforated sheet), a label, a roll, a web, a disc, a kit, a stack, a tablet, and combinations thereof, in any suitable packaging, including, for example, a dispenser, a bag, a box, and a carton.

[0105] To remove the adhesive article from the substrate, at least a portion of the adhesive article is peeled or stretch-released from the substrate. In some embodiments, the stretch angle is 35° or less. In embodiments where a tab is present, a user can grasp the tab and use it to peel or remove the adhesive article from the substrate.

[0106] The adhesive articles may be used to attach a variety of items and objects to surfaces such as painted drywall, plaster, concrete, glass, ceramic, fiberglass, metal, or plastic. Attachable items include, but are not limited to, wall hangers, organizers, holders, baskets, containers, non-slip mats, decorations (e.g., holiday decorations), calendars, posters, dispensers, wire clips, body side moldings on vehicles, handles, road signs, vehicle markings, transportation markings, and signage applications such as reflective sheeting.

[0107] Adhesive articles may be used to attach articles and materials, such as non-slip or wear-resistant mats, to floor surfaces or the bottom of tubs or showers, or to secure items, such as area rugs, to floors. Adhesive articles can be used in a variety of joining and assembly applications, such as adhering at least two containers (e.g., boxes) that will later be separated. Adhesive articles can be used in a variety of cushioning and sound suppression applications, such as cushioning for placement under objects, sound insulation sheeting, vibration dampening, and combinations thereof. Adhesive articles can be used in a variety of closure applications, including container closures (e.g., box closures, food container closures, and beverage container closures), diaper closures, and surgical drape closures. Adhesive articles can be used in a variety of insulation applications. Adhesive articles can be used in a variety of sealing applications, such as gaskets for liquids, vapors (e.g., moisture), and dust. Adhesive articles can be used in a variety of labels, such as removable labels (e.g., notes, price tags, and identification labels on containers), and signs. The adhesive articles can be used in a variety of medical applications (e.g., hospital bandages, markings on medical equipment such as wound care). The adhesive articles can be used in a variety of fastening applications, such as securing one object (e.g., a vase or other fragile object) to another object (e.g., a table or bookshelf). The adhesive articles can be used in a variety of fastening applications, such as securing one or more components of a locking mechanism to a substrate (e.g., a child safety lock can be adhered to a cabinet or cupboard). The adhesive articles can be used in a variety of tamper-indicating applications (e.g., tamper-indicating articles). The adhesive articles can also be incorporated into a variety of other structures, including, but not limited to, abrasive articles (e.g., for sanding), articles for sanding and polishing applications (e.g., buffing pads, disc pads, hand pads, and scouring pads), road marking articles, carpets (e.g., carpet backings), and electronic devices (e.g., securing batteries within housings in cell phones or personal digital assistants (PDAs) to prevent undesired movement).

[0108] The foregoing describes the present disclosure in terms of embodiments that the inventors anticipated and which provided a useful description, but also illustrates that insubstantial, as yet unanticipated, variations of the present disclosure may represent equivalents of the present invention. [Example]

[0109] These examples are for illustrative purposes only and are not meant to limit the scope of the appended claims. Unless otherwise stated or readily apparent from context, all parts, percentages, ratios, etc. in the examples and elsewhere in this specification are by weight.

[0110] material Solvents were obtained from EMD Chemicals (Gibbstown, NJ) unless otherwise noted. [Table 1]

[0111] Test Method Titration method for determining the amine equivalent weight (AEW) of PDMS diamines The amine equivalent weight (AEW) of the PDMS diamine was determined by titration in tetrahydrofuran (THF) with standard HCl (0.1 N) to a bromophenol blue end point.

[0112] Intrinsic viscosity (IV) Intrinsic viscosity measurements were performed at 27° C. on a LAUDA PVS1 viscometer from Lauda-Brinkman (Delran, NJ) using a size 50 capillary viscometer (part number 9721-A00) or on an automated mini PV-HX single-bath dilute polymer viscometer (part number 12.0548) from Cannon Instrument Company (State College, PA) equipped with a size 0B viscometer tube. All polymer samples were analyzed as EtOAc solutions at a concentration of 0.2 grams per deciliter, and IV measurements are reported in deciliters per gram (dL / g).

[0113] Gas chromatography (GC) Gas chromatography analysis was performed on an HP-6890 series instrument using an HP-1 column (30 m × 0.250 mm, 1.0 micron) from Agilent (Santa Clara, CA). Samples were injected neat as 30 wt. % polymer solutions in ethyl acetate.

[0114] Test substrate Drywall panels (obtained from Materials Company, Metzger Building, St. Paul, MN) were painted with Behr PREMIUM PLUS ULTRA® Primer and Paint 2 in 1 Flat Egyptian Nile (FEN) (obtained from Behr Process Corporation, Santa Ana, CA), Sherwin-Williams DURATION® Interior Acrylic Latex Ben Bone White Paint (BB) (obtained from Sherwin-Williams Company, Cleveland, OH), or Valspar Reserve Superior Blue with Satin Sheen (BO) (purchased from Lowes).

[0115] Painting procedure: A first coat of paint was applied to the panel using a paint roller, followed by air drying at ambient conditions for 24 hours. A second coat of paint was applied and allowed to dry at ambient conditions for 24 hours. The panels were placed in a forced air oven set at 50°C for 7 days. The panels were then stored at ambient conditions until use.

[0116] Glass and painted drywall panels measuring 2 in x 2 in (5.1 cm x 5.1 cm) were used for shear strength testing. Glass and painted drywall panels measuring 6 in x 12 in (15.2 cm x 30.5 cm) were used for Peel Adhesion and Package Weight Claim testing at 72°F / 75% RH.

[0117] Static Shear Test Method Static shear strength was determined according to the method of ASTM D3654-82, entitled "Holding Power of Pressure-Sensitive Tapes," with the following modifications. If present, the release liner was removed from the test sample. Test samples measuring 0.5 in x 0.5 in (1.91 cm x 1.91 cm) were adhered to the test substrate via the adhesive composition by passing a 15 lb (6.8 kg) handheld roller twice over the length of the sample at a rate of 12 in / min (30.48 cm / min) at 72°F (22°C) and 50% relative humidity (CTH). A metallized polyester film measuring 0.75 in x 4 in (1.91 cm x 10.16 cm) was adhered to one side of the adhesive test sample for the purpose of attaching a load.

[0118] Test samples were left on the test substrate for 1 hour at 22°C and 50% relative humidity, after which a 2.2 lb (1 kg) weight was applied to the metal-coated polyester film. For high humidity experiments, samples were left on the test substrate for 1 hour at 90°F / 90% RH (32.2°C / 90% RH) in a Thermotron humidity chamber and tested in the same environment throughout the test. The time to failure (in minutes) for all test samples was recorded and reported as an average calculated according to procedures A and C in Chapter 10.1 of the Standard Test Methods. Three samples were tested, and the average time to failure for the three samples and the failure mode for each sample were recorded. If at least one of the three samples had not failed at the end of the test, the value was reported with a "greater than" symbol (i.e., >).

[0119] Package Weight Requirement Test (PWC) Package weight demand testing was performed using multilayer composite tape samples. Testing was performed using a medium-sized COMMAND Utility Hook (Type 17001ES, available from 3M Company, St. Paul, MN). Test samples were cut into 5 / 8 in. x 2 in. (1.6 cm x 5.1 cm) strips. The first adhesive side of the test sample was first applied by hand to a substrate (i.e., painted drywall, tile, or glass) and then adhered to the substrate by passing a 15 lb. (6.8 kg) handheld roller twice over the length of the sample at a speed of 12 in. / min. (30.48 cm / min.). In the next step, the backplate or mounting base of the COMMAND Utility Hook was applied to the side of the test sample opposite the first adhesive side. Finally, the hook was attached to the backplate. The samples were mounted in a vertical position and allowed to rest on the test substrate for 60 minutes at ambient conditions (69-72°F (21-22°C) and 10-40% relative humidity, depending on the time of year), after which a load was attached to the test sample (3 lb weight). The samples were allowed to hang until failure or until 30 days had elapsed. Failure was indicated when the hook article was observed to have completely fallen off the test substrate (the adhesive was no longer adhering to the test substrate surface). Package weight demand data in the tables is provided as weight retention (days). Data is the average of three tests.

[0120] Several package weight tests were conducted on FEN, BB, or BO painted drywall at 72°F / 75% RH using a medium COMMAND utility hook (strip size: 5 / 8" x 2", available from 3M Company).

[0121] Several package weight tests were also conducted in a shower spray chamber at 95% RH with a continuous H2O spray at a water temperature of 105°F to 120°F (41°C to 49°C). A medium COMMAND utility hook (strip size: 5 / 8" x 2", available from 3M Company) was used for this test. The samples were adhered to White Glazed Ceramic Wall Tile (Interceramic, Carrollton, TX), and the load on the sample was 3 lbs.

[0122] Liner peel test The samples were tested in CTH conditions.

[0123] Easy side: A 2.54 cm wide, approximately 20 cm long sample of adhesive transfer tape on a liner was cut using a razor blade. At least four strips of transfer adhesive tape, prepared as described below, were placed on top of each other, overlapping each other, with the adhesive side of each strip in contact with the liner side of the next strip. A stack of at least two strips was applied lengthwise to the plate face of a peel adhesion tester (IMASS SP-2100 tester, available from IMASS, Inc., Accord, MA) using 3M Double Coated Paper Tape 410M (available from 3M Company, St. Paul, MN, USA). The top strip was peeled from the bottom liner at a 180-degree angle, for example, at 60 in / min (152.4 cm / min). The average force required to peel the three strips from their underlying counterparts was recorded as the easy-side liner peel (in grams per inch).

[0124] Tight side: A 2.54 cm wide, approximately 20 cm long sample of the adhesive transfer tape on the liner was cut using a razor blade. The cut sample was applied lengthwise to the plate surface of a peel adhesion tester (IMASS SP-2100 Tester, available from IMASS, Inc., Accord, MA) using 3M Double Coated Paper Tape 410M (available from 3M Company, St. Paul, MN, USA). The release liner was peeled from the adhesive at a 180-degree angle, e.g., at 12 in / min (30.5 cm / min). The average force required to peel the three liners from the adhesive was recorded as the tight-side liner peel (in grams per inch).

[0125] Peel Adhesion Test Peel adhesion testing was performed as follows: First, the vapor-deposited metallized PET was applied to a transfer tape. Then, multiple strips of sample, each 2.54 cm wide and approximately 20 cm long, were cut using a razor blade. After removing the liner, at least three sheets of the PET-backed transfer adhesive tape were applied to a glass substrate and then rolled with a 4.5-pound roller. Unless otherwise noted in the results table, the adhered samples were aged at 72°F (22°C) and 50% RH (CTH) for at least one hour of dwell time before testing. Unless otherwise noted, strips were peeled from the panel using a peel adhesion tester (IMASS SP-2100 tester, available from IMASS, Inc., Accord, MA) at a crosshead speed of 12 in / min (30.5 cm / min). The peel force was measured, and the panel was observed to determine whether any visible adhesive residue remained on the panel. The peel data in the table represents the average of three tests.

[0126] Preparation of adhesive transfer tape The pressure-sensitive adhesive composition was knife coated onto a paper liner web having a fluoroalkyl silicone release surface. The paper liner web speed was 2.75 meters / minute. After coating, the web was passed through an 11-meter long oven with three temperature zones (total residence time: 4 minutes). The temperature in Zone 1 (2.75 meters) was 57°C, the temperature in Zone 2 (2.75 meters) was 80°C, and the temperature in Zone 3 (approximately 5.5 meters) was 93°C. The caliper of the dried adhesive was approximately 2.5-3.0 mils thick. The adhesive transfer tape was then stored at ambient conditions.

[0127] Preparation of multilayer composite tapes Due to shear and package weight requirements, the transfer adhesives of the example set were laminated to a film-foam-film composite and die-cut to the desired size and shape. Specifically, the test adhesive compositions were adhered to both sides of a composite film-foam-film structure similar to that found in COMMAND strip products (31 mil, 6 lb. foam with 1.8 mil polyethylene films on both sides of the foam). Both sides of the film-foam-film structure were pre-primed with 3M Adhesion Promoter 4298UV (3M Company, St. Paul, MN) prior to adhesive lamination.

[0128] Samples of the adhesive coated film-foam-film composite were die cut to 0.5 in x 0.5 in (1.27 cm x 1.27 cm) for shear testing or 5 / 8 in x 2 in (1.59 cm x 5.08 cm) for package weight requirements.

[0129] Copolymers and adhesive compositions Silicone Polyoxamide Copolymer Example 1 Preparation and characterization of silicone polyoxamides using BTFEO in EtOAc solution A 3-gallon jacketed stainless steel reactor equipped with a mechanical stirrer, argon inlet, thermocouple, and dip tube was charged with EtOAc (3972.90 g) and BTFEO (54.55 g). The reactor was placed under positive Ar pressure through a large oil bubbler and stirred at room temperature. With stirring, 13k PDMS diamine was charged (AEW = 6630 g / mol, 1699.88 g, 256.4 mmol of -NH). The reactor was sealed and stirred at room temperature for 1 hour, at which point complete consumption of BTFEO was confirmed by gas chromatography. The jacket temperature was then raised to 70 °C for 30 minutes, followed by the addition of AcOH (0.1945 g) and EDA (5.0735 g). The reactor was sealed under Ar and held at a jacket temperature of 70 °C for 66 hours, at which point a significant increase in the viscosity of the reaction mixture was observed. A sample of the resulting polymer was determined to have an IV of 1.08 dL / g (0.2 g / dL in EtOAc at 27° C.).

[0130] Examples 2 to 6 Novel silicone polyamide copolymers were prepared according to Example 1 using various starting PDMS diamine amine equivalent weights, catalyst amounts, and relative stoichiometries, as summarized in Table 1. [Table 2]

[0131] Example 7 A 3-gallon jacketed stainless steel reactor equipped with a mechanical stirrer, argon inlet, thermocouple, and dip tube was charged with EtOAc (5184 g) and BTFEO (71.3245 g). The reactor was placed under positive Ar pressure through a large oil bubbler and stirred at room temperature. With stirring, 13k PDMS diamine (AEW = 6515 g / mol, 2200.80 g, 337.78 mmol of -NH) was charged. The reactor was sealed and stirred at room temperature for 1 hour, at which point complete consumption of BTFEO was confirmed by gas chromatography, and then AcOH (0.259 g) was added. A portion of this masterbatch was discharged into a 32-oz bottle (523.59 g) and EDA was added (8.1276 g of a toluene solution, 15.34 mmol of -NH). The bottle was sealed and placed in a Launder-O-Meter (available from Atlas Electric Devices Co., Chicago, Ill.) at 70° C. for 60 hours, at which point the contents were cooled to ambient temperature. The reaction yielded a clear, colorless elastomeric solution, which was measured to have an IV of 1.04 dL / g (0.2 g / dL in EtOAc at 27° C.).

[0132] Examples 8 to 10 Novel silicone polyamide copolymers were prepared according to Example 7, targeting different relative stoichiometries to vary the amount of chain extension of the PDMS segments (average p = 1.33 to 2.32), as summarized in Table 2 . [Table 3]

[0133] Example 11 A 12 L resin kettle was charged with BTFEO (94.60 g) and EtOAc (5962 g) under positive nitrogen pressure. The reaction mixture was stirred at room temperature, and 10k PDMS diamine (AEW = 5273 g / mol, 2553 g, 484.13 mmol -NH) was added over 70 minutes. After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours and 45 minutes, at which point complete consumption of the BTFEO was confirmed by gas chromatography. A portion of this masterbatch was added to a 32 oz bottle (579.25 g) and EDA was added (8.6149 g of toluene solution, 17.11 mmol -NH). The bottle was sealed and placed in a Launder-O-Meter (available from Atlas Electric Devices Co., Chicago, Ill.) at 70°C for 36 hours, at which point the contents were cooled to ambient temperature. The reaction yielded a clear, colorless elastomeric solution which was determined to have an IV of 1.09 dL / g (0.2 g / dL in EtOAc at 27° C.).

[0134] Example 12 A 3-gallon jacketed stainless steel reactor equipped with a mechanical stirrer, argon inlet, thermocouple, HYDRAMOTION oscillatory viscometer, and dip tube was charged with EtOAc (4331.69 g) and BTFEO (59.9026 g). The reactor was placed under positive Ar pressure through a large oil bubbler and stirred (200 rpm) at room temperature. With stirring, 13k PDMS diamine (AEW = 6564 g / mol, 1855.03 g, 282.59 mmol of -NH) was charged. The reactor was sealed and stirred at room temperature for 1 hour, at which point complete consumption of BTFEO was confirmed by gas chromatography. The jacket temperature was then increased to 70 °C for 1 hour, followed by the addition of AcOH (0.2119 g) and EDA (5.6623 g). The reactor was sealed under an Ar atmosphere and held at a jacket temperature of 70°C while an in-process viscosity measurement was taken. After 3 hours and 45 minutes, the in-process viscometer read 850 units and additional EDA was charged (0.3933 g). The stirring speed was reduced (96 rpm) and the batch was allowed to cool to room temperature overnight. The reaction yielded a clear, colorless elastomeric solution which was measured to have an IV of 0.953 dL / g (0.2 g / dL in EtOAc at 27°C).

[0135] Formulation of pressure-sensitive adhesives from silicone polyoxamides. Examples 13 to 22 Silicone polyoxamide elastomers were prepared and isolated according to Examples 1 or 11 and formulated as summarized in Table 3. The silicone polyoxamide elastomer was combined with MQ resin (Momentive SR-545, 63% in toluene) to a 50 / 50 elastomer / MQ ratio (w / w dry solids) and diluted to an overall solids content of 35% and a solvent blend of 76 / 24 (w / w) EtOAc / IPA. Shear, liner peel, and peel adhesion data were obtained according to the test methods described above. The data are summarized in Tables 4-6 below. [Table 4] [Table 5] [Table 6] [Table 7]

[0136] Comparative Example 1 BTFEO (2.73 g) and EtOAc (176.73 g) were placed in a 16-oz jar containing a magnetic stir bar. The jar was stirred at room temperature, and 13k PDMS diamine (AEW = 6592.1 g / mol, 75.81 g, 11.50 mmol of -NH) was added portionwise. After the addition was complete, the jar was sealed and stirred at room temperature for 1 hour. Incomplete consumption of BTFEO was confirmed by gas chromatography. The jar was then opened, and AcOH (85 μL) and EDA (2.6790 g of a toluene solution, 9.98 mmol of -NH) were added. The jar was sealed and placed on a roller for 3 days. The reaction yielded a slightly hazy, highly elastic elastomer solution, which was measured to have an IV of 1.36 dL / g (0.2 g / dL in EtOAc at 27 °C).

[0137] The complete disclosures of the publications cited herein are incorporated by reference in their entireties, as if each were individually incorporated. Various modifications and alterations to the present disclosure will become apparent to those skilled in the art without departing from the scope and spirit of the disclosure. It is understood that the present disclosure is not intended to be unduly limited by the exemplary embodiments and examples set forth herein, and that such examples and embodiments are presented merely as examples within the scope of the present disclosure, which is intended to be limited only by the claims set forth herein as follows. The present invention includes the following aspects. (1) at least two repeat units of formula I': [ka] [In the formula, Each R1 is independently alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently an alkylene, an aralkylene, or a combination thereof; Each G is independently a bond or a group of formula R 3 HN-G-NHR 3 Diamine to two -NHR 3 is a divalent residue equivalent to the group excluding Each R 3 are independently hydrogen or alkyl, or R 3 together with G and the nitrogen to which they are both attached form a heterocyclic group; each n is independently an integer from 0 to 300; each p is independently an integer from 1 to 25; each q is independently an integer from 1 to 2, and the average of q is 1.05 or less; The method comprises: (a) Oxalic acid ester of formula II

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Claims

1. At least two repeat units of formula I': 【Chemistry 1】 [In the formula, Each R １ is independently alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halo; each Y is independently an alkylene, an aralkylene, or a combination thereof; Each G is independently a covalent bond or a group of formula R ３ HN-G-NHR ３ From the diamine of ３ is a divalent residue equivalent to the group excluding Each R ３ are independently hydrogen or alkyl, or R ３ together with G and the nitrogen to which they are both attached form a heterocyclic group; each n is independently an integer from 0 to 300; each p is independently an integer from 1 to 25; Each q is independently an integer from 1 to 2, and the average of q is 1.05 or less.

1. A method for producing a copolymer material comprising: The method comprises: (a) an oxalate ester of formula II 【Chemistry 2】 [In the formula, Each R ２ are independently alkyl, haloalkyl, aryl, or alkyl, alkoxy, halo, alkyloxycarbonyl, or a group bonded via N. 【Transformation 3】 (In the formula, each R ４ are independently hydrogen, alkyl, or aryl, or R ４ are aryl substituted with (which together form a ring). to a solvent; (b) mixing the oxalate ester with a polydiorganosiloxane diamine of Formula III 【Chemistry 4】 and reacting until essentially no polydiorganosiloxane diamine or oxalate ester remains, Reaction Product of Formula IV 【Transformation 5】 and forming (c) one or more diamines of formula V 【Transformation 6】 to said reaction product of formula IV to form said repeat unit of formula I'; 10. A method, comprising:

2. 2. The method of claim 1, wherein the oxalic acid ester of formula II is selected from the group consisting of oxalic acid esters of phenol, methyl ethyl ketone oxime, acetone oxime, and trifluoroethanol.

3. 10. The method of claim 1, wherein the molar ratio of the oxalate ester of Formula II to the polydiorganosiloxane diamine of Formula III is at least 1:0.

56.

4. 2. The method of claim 1, wherein the molar ratio of the polydiorganosiloxane diamine of formula III to the diamine of formula V to the oxalate ester of formula II is 0.6:0.4:1.

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