Carbo-silane functional silicones

Abstract

The present disclosure relates to novel polysiloxanes and a method for preparation of such polysiloxanes. The polysiloxanes disclosed herein are polydimethylsiloxane (PDMS)-based copolymers having at least one reactive group and at least one non-reactive group. The PDMS-based copolymers are characterized by the presence of at least one reactive group at the terminal and / or pendant positions.

Description

CARBO-SILANE FUNCTIONAL SILICONES TECHNICAL FIELD

[0001] The present disclosure relates to technical field of silicone materials. In particular, the present disclosure relates to modified polysiloxanes and to a method of preparing such polysiloxanes. BACKGROUND

[0002] The background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.

[0003] Additives with special properties such as hydrophobicity, oleophobicity, resistance to chemical, corrosion and weathering have been developed in the recent past and have received much attention in the art. Fluoropolymers are one of the major additives used in the industry. Conventional fluoropolymers include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), fluorinated ethylene propylene copolymers (FEP), ethylene tetrafluoroethylene copolymers (ETFE) and fluoroethylene vinyl ether (FEVE). Due to environmental concerns, there is a growing need for non-fluoro alternatives.

[0004] Therefore, it is readily apparent that there exists a need for new and improved additives which maintain a balance between hydrophobicity and hydrophilicity and contain at least one reactive functional group. The present disclosure satisfies these needs and provides further related advantages. SUMMARY

[0005] The following presents a summary of this disclosure to provide a basic understanding of some aspects of the invention. This summary is intended to neither identify key or critical elements nor define any limitations of embodiments or claims. Furthermore, this summary may provide a simplified overview of some aspects that may be described in greater detail in other portions of this disclosure.1 35816120.1

[0006] The present disclosure relates to novel polysiloxanes that are useful as additives in various formulations, as well as methods for their preparation. The disclosed polysiloxanes are polydimethylsiloxanes (PDMS) featuring at least one reactive functional group. These reactive functional groups may include, but are not limited to, alkoxy, trimethoxysilane, hydroxy, epoxy, vinyl hydride, acrylate, isocyanate, or amine groups. Additionally, the polysiloxanes incorporate at least one non-reactive group, such as trialkylsilane, alkyl, or phenyl. The PDMS-based copolymers are characterized by the presence of at least one reactive functional group positioned at the terminal and / or pendant sites within the polymer structure.

[0007] In one embodiment, the disclosure provides polysiloxanes having the following Formula (I):wherein m = 1 to 100; n = 1 to 100; p = 1 to 100; m + n + p = 5 to 100; m / n = 0.5 to 20; m / p = 0.5 to 20; X= 0 to 20; R1, R2and R3represent, independently of one another, H, an alkenyl group, an alkyl group, a cycloalkyl group, an aromatic group, a heteroaromatic group, a bicyclic group, -Si(OM)3, -CH2CH2Si(OM)3, - Si(Y)3,alkoxy, amino, epoxy, acrylate, hydroxy, thiol, carboxy, or isocyanate; where, M is an alkyl group;2 35816120.1Y is selected from an alkyl group, a cycloalkyl group, an aromatic group, a heteroaromatic group, a bicyclic group, and an aliphatic fused ring; R4is -CH3or -C2H5; provided that when R2and R3are each -Si(CH3)3, then R4 is -CH2CH2Si(OCH3)3.

[0008] In some embodiments, in Formula I, at least one of R1, R2and R3is a reactive group.

[0009] In some embodiments, in Formula I, R2and R3are reactive groups.

[0010] In some embodiments, in Formula I, at least one of R1, R2 and R3 is a trialkylsilane.

[0011] In another embodiment, the disclosure provides polysiloxanes having the following Formula II:m + n = 5 to 100; m / n = 0.5 to 20; Q is selected from the group consisting of3 35816120.1ving the following Formula (III):wherein m = 1 to 100; n = 1 to 100; m + n = 5 to 100; m / n = 0.5 to 20; Z is selected from the group consisting ofof the polysiloxanes of Formula (I), (II) and (III).

[0014] Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments.4 35816120.1DETAILED DESCRIPTION

[0015] The following is a detailed description of embodiments of the present disclosure. The embodiments are in such detail as to clearly communicate the disclosure. However, the amount of detail offered is not intended to limit the anticipated variations of embodiments; on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.

[0016] Embodiments herein are directed to novel polysiloxanes that are useful as additives in various formulations. The disclosed polysiloxanes are polydimethylsiloxanes (PDMS) featuring at least one reactive functional group. These reactive functional groups may include, but are not limited to, alkoxy, trimethoxysilane, hydroxy, epoxy, vinyl hydride, acrylate, isocyanate, or amine groups. Additionally, the polysiloxanes incorporate at least one non-reactive group, such as trialkylsilane, alkyl, or phenyl. The PDMS-based copolymers are characterized by the presence of at least one reactive functional group positioned at the terminal and / or pendant sites within the polymer structure.

[0017] In one embodiment, the polysiloxanes have the following Formula (I):wherein m = 1 to 100; n = 1 to 100; p = 1 to 100; m + n + p = 5 to 100; m / n = 0.5 to 20; m / p = 0.5 to 20; X= 0 to 20;5 35816120.1R1, R2 and R3 represent, independently of one another, H, an alkenyl group, an alkyl group, a cycloalkyl group, an aromatic group, a heteroaromatic group, a bicyclic group, -Si(OM)3, -CH2CH2Si(OM)3, - Si(Y)3,alkoxy, amino, epoxy, acrylate, hydroxy, thiol, carboxy, or isocyanate; where, M is an alkyl group; Y is selected from an alkyl group, a cycloalkyl group, an aromatic group, a heteroaromatic group, a bicyclic group, and an aliphatic fused ring; R4 is -CH3 or -C2H5; provided that when R2 and R3 are each -Si(CH3)3, then R4is -CH2CH2Si(OCH3)3.

[0018] In some embodiments, in Formula I, at least one of R1, R2 and R3 is a reactive group.

[0019] In some embodiments, in Formula I, R2 and R3 are reactive groups.

[0020] In some embodiments, in Formula I, at least one of R1, R2 and R3 is a trialkylsilane.

[0021] In an embodiment, the polysiloxane is a reacted resin which is a reaction product of polysiloxane of Formula I with a resin.

[0022] The term “alkyl” as used herein refers to a straight-chain or branched- chain alkyl radical containing from 1 to 20, preferably 1 to 10, and more preferably 1 to 6, carbon atoms. With particular preference the term “alkyl” stands for methyl or ethyl.

[0023] The term “cycloalkyl” as used herein refers to a saturated or partially unsaturated (for example, a cycloalkenyl group) cyclic group that contains one or more rings, and contains from 3 to 14 ring carbon atoms, preferably from 3 to 10 ring carbon atoms.

[0024] The aromatic group contains one or more rings containing from 6 to 14 ring carbon atoms, preferably from 6 to 10 ring carbon atoms. The aromatic group refers furthermore to groups that are substituted by fluorine, chlorine, bromine or6 35816120.1iodine atoms or by OH, SH, NH2, N3 or NO2 groups. Examples are the phenyl, naphthyl, biphenyl or anilinyl.

[0025] The heteroaromatic group contains one or more rings containing from 5 to 14 ring atoms, preferably from 5 to 10 ring atoms, and contains one or more oxygen, nitrogen, phosphorus or sulfur ring atoms, preferably O, S or N.

[0026] The term “bicyclic” as used herein refers to a bicyclic ring system, i.e. carbocyclic or heterocyclic, saturated or having one or more units of unsaturation, having one or more atoms in common between the two rings of the ring system. Thus, the term includes any permissible ring fusion, such as ortho-fused or spirocyclic.

[0027] In various embodiments, the length of the PDMS co-polymer is controlled to maintain a total unit (m + n + p) variation within the range of 5 to 100.

[0028] Preferably, the ratio of m to n and the ratio of m to p in the polysiloxane of formulae (I), (II) and (III) is in the range of 0.5:1 to 20:1. Such ratios are highly advantageous in that they impart for example hydrophobic / oleophobic characteristics to the polymer.

[0029] In one embodiment, R4 is -CH2CH2Si (OCH3)3; and R2 and R3 are each -Si(CH3)3.

[0030] In cases where R4 is -CH3 and R2 = R3, the substituent R1 may be distinct and independently selected. Alternatively, if R2and R3represent reactive groups (e.g., -Si(OM)3), the substituent R1 may be the non-reactive silane -Si(Y)3, and vice versa. In some embodiments, R2and R3may constitute a combination of reactive silane (e.g., -Si(OM)3 or -CH2CH2Si(OM)3) and non-reactive silane (e.g., -Si(Y)3).

[0031] In one embodiment, R4 is -CH2CH2Si(OCH3)3; R2 and R3 are each - Si(CH3)3; and R1is -Si(Y)3.

[0032] In another embodiment, the polysiloxanes have the following Formula (II):7 35816120.1wherein m = 1 to 100; n = 1 to 100; m + n = 5 to 100; m / n = 0.5 to 20; Q is selected from the group consisting of(III):8 35816120.1wherein m = 1 to 100; n = 1 to 100; m + n = 5 to 100; m / n = 0.5 to 20; Z is selected from the group consisting ofof the polysiloxanes of Formula (I), (II) and (III).

[0035] In some embodiments, the polysiloxane of Formula (I) has the structure of Formula (Ia) which can be prepared according to the reaction Scheme 1 set out below:Scheme 1 wherein m, n and p are as defined above for Formula I.9 35816120.1Scheme 1 illustrates a process for the preparation of Formula (Ia), comprising the reaction of formula (IV) with trimethoxyvinylsilane in the presence of a Karstedt catalyst.

[0036] In various embodiments, the pendant hydride of Formula (IV) can be prepared according to the reaction Scheme-1A set out below:Scheme 1A

[0037] In various embodiments, the Formula (V) can be prepared according to the reaction Scheme-1B set out below:10 35816120.1Scheme 1B

[0038] In various embodiments, the polysiloxanes of Formula II can be prepared according to the reaction Scheme 2 set out below:Scheme 2 wherein m, n and Q are as defined above for Formula II. Scheme 2 illustrates a process for the preparation of Formula (II), comprising first reacting Formula (VII) with trimethoxyvinylsilane in the presence of a Karstedt catalyst to form an intermediate, and then reacting the intermediate with . The intermediate has the following structural formula:

[0039] InVII can be prepared according to the reaction Scheme 2A shown below:11 35816120.1I) Scheme 2A

[0040] In various embodiments, the D4* can be prepared according to the reaction Scheme 2B shown below:

[0041] In various embodiments, the polysiloxanes of Formula III can be prepared according to the reaction Scheme 3 set out below:Formula (VII) Formula (III) Scheme 3 wherein m, n and Z are as defined above for Formula III. Scheme 3 illustrates a process for the preparation of Formula (III), comprising first reacting Formula (VII) with trimethoxyvinylsilane in the presence of a Karstedt catalyst to form an intermediate, and then reacting the intermediate with . The intermediate has the following structural formula:12 35816120.1

[0042] Whi embodiments of the disclosure, other and further embodiments of the invention may be devised without departing from the basic scope of the disclosure. The invention is not limited to the described embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art. EXAMPLES

[0043] The present disclosure is further explained in the form of following examples. However, it is to be understood that the following examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention. The appropriate procedure to prepare the fragrance compositions will be apparent to those skilled in the art. Synthesis of PDMS co-polymer having hydrophobic / oleophobic groups:

[0044] Example 1 - Synthesis of bis-hydride terminated PDMS co- polymer Step-113 35816120.1D flask (R.B.) equipped with a chilled water condenser, a thermometer, and a pressure- equalizing addition funnel. The apparatus was purged with nitrogen to establish an inert atmosphere. The reaction vessel was then heated to 60 °C. Karstedt catalyst (2 ppm) was meticulously added to the D4-H, followed by a thorough nitrogen purge. Subsequently, vinyltrimethylsilane (0.44 moles, 4 equivalents) was introduced dropwise into the reaction mixture. An exothermic reaction was observed after few minutes, and the addition rate was carefully controlled to maintain the internal temperature below 75 °C. Vigorous reflux of vinyltrimethylsilane was observed. The reaction was allowed to proceed for 1 more hour, during which the temperature naturally decreased to 60 °C. A sample was collected NMR analysis, confirming the consumption of Si-H and the formation of new Si-CH2 linkages. The reaction mixture was then subjected to vacuum distillation at 100 °C for 1 hour under high-vacuum conditions (0 psi) to remove volatile components and unreacted vinyltrimethylsilane. Step-2: Acid-catalyzed ring opening polymerization (ROP)14 35816120.1Compound HMMH (2.14 g, 1.59 mmol), D4 (10 g, 2.11 mmol) and D4* (5 g, 0.48 mmol) was taken in a R.B and was charged with Amberlyst 15 (350 mg, 2 wt%) catalyst at RT and was stirred for 8 h at RT. Solid content was checked at this point which showed 86%. It was subjected to vacuum distillation at 100 °C for 1 hour under high-vacuum conditions (0 psi) to remove volatile components and was used for next hydrosilylation reaction. By following same procedure loading of HMMH was varied to get different chain length. Also, weight ratios of D4 and D4* were changed to synthesize different co-polymers having different -Si(Me)3 loading. Step-3A: Synthesis of additive containing reactive trimethoxysilane and non- reactive silanen = 5 to 100) was accurately weighed and placed in a three-neck round-bottom flask (R.B.) equipped with a chilled water condenser, a thermometer, and a pressure-15 35816120.1equalizing addition funnel. The apparatus was purged with nitrogen to establish an inert atmosphere. The reaction vessel was then heated to 60 °C. Karstedt catalyst (2 ppm) was meticulously added to the PDMS bis-hydride solution, followed by a thorough nitrogen purge. Subsequently, trimethoxyvinylsilane (0.55 moles, 1.1 equivalents) was introduced dropwise into the reaction mixture. An immediate exothermic reaction was observed, and the addition rate was carefully controlled to maintain the internal temperature below 75 °C. The reaction was allowed to proceed for 30 minutes, during which the temperature naturally decreased to 60 °C. A sample was collected NMR analysis, confirming the partial consumption of bis-silyl hydride and the formation of new Si-CH2 linkages. Following this, trimethylvinylsilane (0.55 moles, 1.1 equivalents) was introduced dropwise through an addition funnel at a controlled rate, ensuring that the exothermic reaction did not exceed 75 °C. After an additional 30 minutes, NMR analysis indicated the complete consumption of bis-silyl hydride. The reaction mixture was then subjected to vacuum distillation at 100 °C for 1 hour under high-vacuum conditions (0 psi) to remove volatile components. The resulting product was utilized in coating formulation. Step-3B: Synthesis of additive containing reactive trimethoxysilane and non- reactive aliphatic / aromatic alkene moietyn = 5 to 100) was accurately weighed and placed in a three-neck round-bottom flask16 35816120.1(R.B.) equipped with a chilled water condenser, a thermometer, and a pressure- equalizing addition funnel. The apparatus was purged with nitrogen to establish an inert atmosphere. The reaction vessel was then heated to 60 °C. Karstedt catalyst (2 ppm) was meticulously added to the PDMS bis-hydride-1 solution, followed by a thorough nitrogen purge. Subsequently, trimethoxyvinylsilane (0.55 moles, 1.1 equivalents) was introduced dropwise into the reaction mixture. An immediate exothermic reaction was observed, and the addition rate was carefully controlled to maintain the internal temperature below 75 °C. The reaction was allowed to proceed for 30 minutes, during which the temperature naturally decreased to 60 °C. A sample was collected NMR analysis, confirming the partial consumption of bis-silyl hydride and the formation of new Si-CH2linkages. Following this, Dodecene (0.55 moles, 1.1 equivalents) was introduced dropwise through an addition funnel and then heated at 80oC for 1 h. NMR analysis indicated the complete consumption of bis-silyl hydride. The reaction mixture was then subjected to vacuum distillation at 100 °C for 1 hour under high-vacuum conditions (0 psi) to remove volatile components. The resulting product was utilized in coating formulation.

[0045] Example 2 - Synthesis of pendant hydride containing PDMS co- polymer Step-1round- bottom flask (R.B.) equipped with a chilled water condenser, a thermometer, and a pressure-equalizing addition funnel. The apparatus was purged with nitrogen to establish an inert atmosphere. The reaction vessel was then heated to 60 °C.17 35816120.1Karstedt catalyst (2 ppm) was meticulously added to the HMMH, followed by a thorough nitrogen purge. Subsequently, vinyltrimethylsilane (0.22 moles, 2.2 equivalents) was introduced dropwise into the reaction mixture. An exothermic reaction was observed immediately, and the addition rate was carefully controlled to maintain the internal temperature below 75 °C. Vigorous reflux of vinyltrimethylsilane was observed. The reaction was allowed to proceed for 1 more hour, during which the temperature naturally decreased to 60 °C. A sample was collected NMR analysis, confirming the consumption of Si-H and the formation of two new Si-CH2 linkages, thereby formation of MM*. The reaction mixture was then subjected to vacuum distillation at 100 °C for 1 hour under high- vacuum conditions (0 psi) to remove volatile components and unreacted vinyltrimethylsilane. Step-2g, 5.9, 1 equivalent) was taken in a R.B and was charged with Amberlyst 15 (350 mg, ~2 wt%) catalyst at RT and was stirred for 8 h at RT. Solid content was checked at this point which showed 86%. It was subjected to vacuum distillation at 100 °C for 1 hour under high-vacuum conditions (0 psi) to remove volatile components and was used for next hydrosilylation reaction. By following same procedure, loading of MM* was varied to get different chain length. Also, weight ratios of D4, D4* and D4-H were changed to synthesize different co-polymers having different -Si(Me)3 and Si-H loading. Step-3: Synthesis of additive containing reactive pendant trimethoxysilane and non-reactive terminal trimethylsilane18 35816120.1ck round-bottom flask (R.B.) equipped with a chilled water condenser, a thermometer, and a pressure-equalizing addition funnel. The apparatus was purged with nitrogen to establish an inert atmosphere. The reaction vessel was then heated to 60 °C. Karstedt catalyst (2 ppm) was meticulously added to the it, followed by a thorough nitrogen purge. Subsequently, trimethoxyvinylsilane (excess) was introduced dropwise into the reaction mixture. An exothermic reaction was observed immediately, and the addition rate was carefully controlled to maintain the internal temperature below 75 °C. The reaction was allowed to proceed for 1 more hour, during which the temperature naturally decreased to 60 °C. A sample was collected NMR analysis, confirming the consumption of all Si-H and the formation of two new Si-CH2linkages. The reaction mixture was then subjected to vacuum distillation at 100 °C for 1 hour under high-vacuum conditions (0 psi) to remove volatile components and unreacted silanes. This was then further used for coating applications.19 35816120.1

Claims

We Claim:

1. A polysiloxane of Formula (I):m = 1 to 100; n = 1 to 100; p = 1 to 100; m + n + p = 5 to 100; m / n = 0.5 to 20; m / p = 0.5 to 20; X= 0 to 20; R1, R2and R3represent, independently of one another, H, an alkenyl group, an alkyl group, a cycloalkyl group, an aromatic group, a heteroaromatic group, a bicyclic group, -Si(OM)3, -CH2CH2Si(OM)3, - Si(Y)3, alkoxy, amino, epoxy, acrylate, hydroxy, thiol, carboxy, or isocyanate; where, M is an alkyl group; Y is selected from an alkyl group, a cycloalkyl group, an aromatic group, a heteroaromatic group, a bicyclic group, and an aliphatic fused ring; R4 is -CH3 or -C2H5; provided that when R2 and R3 are each -Si(CH3)3, then R4is -CH2CH2Si(OCH3)3.

2. The polysiloxane of Formula (I) as claimed in claim 1, wherein at least one of R1, R2 and R3 is a reactive group; or wherein R2 and R3 are reactive groups; or wherein at least one of R1, R2 and R3 is a trialkylsilane.20 35816120.

13. The polysiloxane of Formula (I) as claimed in claim 1, wherein R4 is - CH2CH2Si(OCH3)3; and R2and R3are each -Si(CH3)3.

4. The polysiloxane of Formula (I) as claimed in claim 1, wherein R4is - CH2CH2Si(OCH3)3; R2 and R3 are each -Si(CH3)3; and R1 is -Si(Y)3.

5. A polysiloxane of Formula (II):wherein, m = 1 to 100; n = 1 to 100; m + n = 5 to 100; m / n = 0.5 to 20; Q is selected from the group consisting of21 35816120.1wherein, m = 1 to 100; n = 1 to 100; m + n = 5 to 100; m / n = 0.5 to 20; Z is selected from the group consisting of, (IV) with trimethoxyvinylsilane in presence of a Karstedt catalyst,wherein m, n and p are as defined above for Formula I.

8. A process for preparation of Formula (II), comprising first reacting formula (VII) with trimethoxyvinylsilane in presence of a Karstedt catalyst to form an intermediate and then reacting the intermediate with ,22 35816120.

19. A process for preparation of Formula (III), comprising first reacting formula (VII) with trimethoxyvinylsilane in presence of a Karstedt catalyst to form an intermediate and then reacting the intermediate with ,wherein m, n and Z are as defined above for Formula III.23 35816120.1