Carbon-silane functionalized silicones

Abstract

This disclosure relates to novel polysiloxanes and methods for preparing such polysiloxanes. The polysiloxanes disclosed herein are copolymers based on polydimethylsiloxane (PDMS) 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 overhang positions.

Description

Technical Field

[0001] This disclosure relates to the field of organosilicon materials technology. Specifically, this disclosure relates to modified polysiloxanes and methods for preparing such polysiloxanes. Background Technology

[0002] This background description includes information that may help in understanding the invention. It does not imply an admission that any information provided herein is prior art or related to the currently claimed invention, nor does it imply an admission that any publication specifically or implicitly referenced is prior art.

[0003] In recent years, additives with special properties such as hydrophobicity, oleophobicity, chemical resistance, corrosion resistance, and weather resistance have been developed and have attracted much attention in this field. Fluoropolymers are one of the main additives used in industry. Common fluoropolymers include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), fluorinated ethylene propylene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), and fluoroethylene vinyl ether (FEVE). Due to environmental concerns, the demand for fluorine-free alternatives is increasing.

[0004] Therefore, it is readily apparent that there is a need for novel and improved additives that maintain a balance between hydrophobicity and hydrophilicity and contain at least one reactive functional group. This disclosure meets these needs and provides further related advantages. Summary of the Invention

[0005] The following is an overview of this disclosure to provide a basic understanding of some aspects of the invention. This overview is not intended to identify key or important elements, nor is it intended to impose any limitations on the implementation or claims. Furthermore, this overview provides a simplified overview of aspects that are described in more detail in other parts of this disclosure.

[0006] This disclosure relates to novel polysiloxanes that can be used as additives in various formulations and methods for their preparation. The disclosed polysiloxanes are polydimethylsiloxanes (PDMS) characterized by at least one reactive functional group. These reactive functional groups may include, but are not limited to, alkoxy, trimethoxysilane, hydroxyl, epoxy, vinyl hydride, acrylate, isocyanate, or amino groups. Furthermore, the polysiloxane is incorporating at least one non-reactive group, such as a trialkylsilane, alkyl, or phenyl group. PDMS-based copolymers are characterized by the presence of at least one reactive functional group at the ends and / or overhang sites within the polymer structure.

[0007] In one embodiment, this disclosure provides a polysiloxane having the following formula (I):

[0008]

[0009] in

[0010] m = 1 to 100; n = 1 to 100; p = 1 to 100;

[0011] m+n+p=5 to 100;

[0012] m / n = 0.5 to 20;

[0013] m / p = 0.5 to 20;

[0014] X = 0 to 20;

[0015] R1, R2, and R3 independently represent H, alkenyl, alkyl, cycloalkyl, aromatic group, heteroaromatic group, bicyclic group, -Si(OM)3, -CH2CH2Si(OM)3, -Si(Y)3, alkoxy, amino, epoxy, acrylate, hydroxyl, mercapto, carboxyl, or isocyanate.

[0016] in,

[0017] M is an alkyl group;

[0018] Y is selected from alkyl, cycloalkyl, aromatic groups, heteroaromatic groups, bicyclic groups, and aliphatic fused rings;

[0019] R4 is -CH3 or -C2H5; the condition is that when R2 and R3 are each -Si(CH3)3, then R4 is -CH2CH2Si(OCH3)3.

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

[0021] In some embodiments, R2 and R3 are reactive groups in Formula I.

[0022] In some embodiments, in Formula I, at least one of R1, R2 and R3 is a trialkylsilane.

[0023] In another embodiment, this disclosure provides a polysiloxane having the following formula II:

[0024]

[0025] in

[0026] m = 1 to 100; n = 1 to 100;

[0027] m+n = 5 to 100;

[0028] m / n = 0.5 to 20;

[0029] Q is selected from:

[0030] , , , , , , , , , , ,as well as .

[0031] In another embodiment, this disclosure provides a polysiloxane having the following formula (III):

[0032]

[0033] in

[0034] m = 1 to 100; n = 1 to 100;

[0035] m+n = 5 to 100;

[0036] m / n = 0.5 to 20;

[0037] Z is selected from:

[0038] , , , , ,as well as .

[0039] This disclosure also provides processes for preparing polysiloxanes of formulas (I), (II) and (III).

[0040] The various objects, features, aspects, and advantages of the subject matter of the present invention will become clearer from the following detailed description of preferred embodiments. Detailed Implementation

[0041] The following is a detailed description of embodiments of this disclosure. These embodiments are described in detail sufficient to clearly convey the contents of this disclosure. However, the amount of detail provided is not intended to limit contemplative variations in the embodiments; rather, it is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of this disclosure as defined by the appended claims.

[0042] The embodiments described herein relate to novel polysiloxanes that can be used as additives in various formulations. The disclosed polysiloxanes are polydimethylsiloxanes (PDMS) characterized by at least one reactive functional group. These reactive functional groups may include, but are not limited to, alkoxy, trimethoxysilane, hydroxyl, epoxy, vinyl hydride, acrylate, isocyanate, or amino groups. Furthermore, the polysiloxane is incorporated with at least one non-reactive group, such as a trialkylsilane, alkyl, or phenyl group. PDMS-based copolymers are characterized by the presence of at least one reactive functional group at the ends and / or overhang sites within the polymer structure.

[0043] In one embodiment, the polysiloxane has the following formula (I):

[0044]

[0045] in

[0046] m = 1 to 100; n = 1 to 100; p = 1 to 100;

[0047] m+n+p=5 to 100;

[0048] m / n = 0.5 to 20;

[0049] m / p = 0.5 to 20;

[0050] X = 0 to 20;

[0051] R1, R2, and R3 independently represent H, alkenyl, alkyl, cycloalkyl, aromatic group, heteroaromatic group, bicyclic group, -Si(OM)3, -CH2CH2Si(OM)3, -Si(Y)3, alkoxy, amino, epoxy, acrylate, hydroxyl, mercapto, carboxyl, or isocyanate.

[0052] in,

[0053] M is an alkyl group;

[0054] Y is selected from alkyl, cycloalkyl, aromatic groups, heteroaromatic groups, bicyclic groups, and aliphatic fused rings;

[0055] R4 is -CH3 or -C2H5; the condition is that when R2 and R3 are each -Si(CH3)3, then R4 is -CH2CH2Si(OCH3)3.

[0056] In some embodiments, in Formula I, at least one of R1, R2 and R3 is a reactive group.

[0057] In some embodiments, R2 and R3 are reactive groups in Formula I.

[0058] In some embodiments, in Formula I, at least one of R1, R2 and R3 is a trialkylsilane.

[0059] In one embodiment, the polysiloxane is a reacted resin, wherein the reacted resin is a reaction product of the polysiloxane of Formula I and a resin.

[0060] As used herein, the term "alkyl" refers to a straight-chain or branched alkyl group containing 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms. Particularly preferably, the term "alkyl" means methyl or ethyl.

[0061] As used herein, the term "cycloalkyl" refers to a saturated or partially unsaturated (e.g., cycloalkenyl) cyclic group containing one or more rings and 3 to 14 cyclic carbon atoms, preferably 3 to 10 cyclic carbon atoms.

[0062] An aromatic group contains one or more rings containing 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. An aromatic group also refers to a group substituted with fluorine, chlorine, bromine, or iodine atoms, or with OH, SH, NH2, N3, or NO2 groups. Examples include phenyl, naphthyl, biphenyl, or aniline.

[0063] The heteroaromatic group contains one or more rings with 5 to 14 ring atoms, preferably 5 to 10 ring atoms, and contains one or more ring atoms of oxygen, nitrogen, phosphorus or sulfur, preferably O, S or N.

[0064] As used herein, the term "bicyclic" refers to a bicyclic ring system, that is, a carbocyclic or heterocyclic system, saturated or having one or more unsaturated units, wherein one or more atoms are shared between the two rings. Therefore, the term includes any permitted ring fusion, such as ortho-fused or spirocyclic fusion.

[0065] In various implementations, the length of the PDMS copolymer is controlled so that the variation in total units (m+n+p) is kept within the range of 5 to 100.

[0066] Preferably, the ratio of m to n and the ratio of m to p in the polysiloxanes of formulas (I), (II), and (III) are in the range of 0.5:1 to 20:1. Such ratios are highly advantageous because they impart hydrophobic / oleophobic properties to the polymer, for example.

[0067] In one embodiment, R4 is -CH2CH2Si(OCH3)3; and R2 and R3 are each -Si(CH3)3.

[0068] In cases where R4 is -CH3 and R2 = R3, the substituent R1 can be different and chosen independently. Alternatively, if R2 and R3 represent reactive groups (e.g., -Si(OM)3), then the substituent R1 can be a non-reactive silane -Si(Y)3, and vice versa. In some embodiments, R2 and R3 can constitute a combination of reactive silanes (e.g., -Si(OM)3 or -CH2CH2Si(OM)3) and non-reactive silanes (e.g., -Si(Y)3).

[0069] In one embodiment, R4 is -CH2CH2Si(OCH3)3; R2 and R3 are each -Si(CH3)3; and R1 is -Si(Y)3.

[0070] In another embodiment, the polysiloxane has the following formula (II):

[0071]

[0072] in

[0073] m = 1 to 100; n = 1 to 100;

[0074] m+n = 5 to 100;

[0075] m / n = 0.5 to 20;

[0076] Q is selected from

[0077] , , , , , , , , , , ,as well as .

[0078] In another embodiment, the polysiloxane has the following formula (III):

[0079]

[0080] in

[0081] m = 1 to 100; n = 1 to 100;

[0082] m+n = 5 to 100;

[0083] m / n = 0.5 to 20;

[0084] Z is selected from

[0085] , , , , ,as well as .

[0086] This disclosure also provides processes for preparing polysiloxanes of formulas (I), (II) and (III).

[0087] In some embodiments, the polysiloxane of formula (I) has the structure of formula (Ia), which can be prepared according to reaction scheme 1 as shown below:

[0088]

[0089] Option 1

[0090] Where m, n, and p are defined as described above with respect to Equation I.

[0091] Scheme 1 illustrates a process for preparing formula (Ia), which involves reacting formula (IV) with trimethoxyvinylsilane in the presence of a Karstedt catalyst.

[0092] In various embodiments, the pendant hydride of formula (IV) can be prepared according to reaction scheme-1A as shown below:

[0093]

[0094] Option 1A

[0095]

[0096] In various embodiments, formula (V) can be prepared according to reaction scheme-1B as shown below:

[0097]

[0098] Option 1B

[0099] In various embodiments, the polysiloxane of formula II can be prepared according to reaction scheme 2 as shown below:

[0100]

[0101] Option 2

[0102] Where m, n and Q are defined as in Equation II above.

[0103] Scheme 2 illustrates a process for preparing 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 reaction. The intermediate has the following structural formula:

[0104]

[0105] In various embodiments, the di-hydride of formula VII can be prepared according to reaction scheme 2A as shown below:

[0106]

[0107] Option 2A

[0108] In various implementations, D4 It can be prepared according to reaction scheme 2B as shown below:

[0109]

[0110] Option 2B

[0111] In various embodiments, the polysiloxane of formula III can be prepared according to reaction scheme 3 as shown below:

[0112]

[0113] Option 3

[0114] Where m, n and Z are as defined above with respect to Equation III.

[0115] Scheme 3 illustrates a process for preparing 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 reaction. The intermediate has the following structural formula:

[0116]

[0117] While the foregoing description discloses various embodiments of this disclosure, other and further embodiments of the invention may be conceived without departing from the basic scope of this disclosure. The invention is not limited to the described embodiments, styles, or examples, but is included in conjunction with information and knowledge available to those skilled in the art to enable them to make and use the invention.

[0118] Example

[0119] The present disclosure is further illustrated by the following embodiments. However, it should be understood that the following embodiments are merely illustrative and should not be considered as limiting the scope of the invention. Various variations and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such variations and modifications can be made without departing from the scope of the invention. Suitable procedures for preparing fragrance compositions will be apparent to those skilled in the art.

[0120] Synthesis of PDMS copolymers with hydrophobic / oleophobic groups:

[0121] Example 1 – Synthesis of PDMS copolymers terminated by bis-hydride

[0122] Step-1

[0123]

[0124] Weigh 0.1 mol of D4-H and place it in a three-necked round-bottom flask (RB) equipped with a cooling water condenser, a thermometer, and a pressure-equalizing addition funnel. Purge the apparatus with nitrogen to establish an inert atmosphere. Then heat the reaction vessel to 60°C.

[0125] The Karstedt catalyst (2 ppm) was carefully added to D4-H, followed by thorough nitrogen purging. Then, vinyltrimethylsilane (0.44 mol, 4 equivalents) was introduced dropwise into the reaction mixture. An exothermic reaction was observed after several minutes, and the addition rate was carefully controlled to keep the internal temperature below 75 °C. Vigorous reflux of vinyltrimethylsilane was observed. The reaction was allowed to proceed for 1 hour, during which time the temperature naturally decreased to 60 °C. Samples were collected for NMR analysis, confirming the consumption of Si-H and the formation of new Si-CH2 bonds. The reaction mixture was then vacuum distilled at 100 °C for 1 hour under high vacuum (0 psi) to remove volatile components and unreacted vinyltrimethylsilane.

[0126] Step 2: Acid-catalyzed ring-opening polymerization (ROP)

[0127]

[0128] The mixtures HMMH (2.14 g, 1.59 mmol), D4 (10 g, 2.11 mmol) and D4 (5 g, 0.48 mmol) was placed in RB, and Amberlyst 15 (350 mg, 2 wt%) catalyst was added under RT, and the mixture was stirred under RT for 8 hours. The solid content was then measured and showed to be 86%. The mixture was then vacuum distilled at 100 °C for 1 hour under high vacuum (0 psi) to remove volatile components and used in the subsequent hydrosilylation reaction.

[0129] Different chain lengths can be obtained by varying the HMMH load amount using the same procedure. Additionally, D4 and D4 can be changed. The weight ratio was adjusted to synthesize different copolymers with different Si(Me)3 loadings.

[0130] Step 3A: Synthesis of additives containing reactive trimethoxysilanes and non-reactive silanes

[0131]

[0132] The vinylsilane used ( Representative list of )

[0133] , , , , , , , , , , ,as well as .

[0134] Procedure: Accurately weigh 0.5 mol of PDMS di-hydride-1 (where the variable chain length n = 5 to 100) into a three-necked round-bottom flask (RB) equipped with a cooling water condenser, thermometer, and pressure-balanced feeding funnel. Purge the apparatus with nitrogen to establish an inert atmosphere. Then heat the reaction vessel to 60°C.

[0135] The Karstedt catalyst (2 ppm) was carefully added to a PDMS bis-hydride solution, followed by thorough nitrogen purging. Trimethoxyvinylsilane (0.55 mol, 1.1 equivalent) was then introduced dropwise into the reaction mixture. An immediate exothermic reaction was observed, and the addition rate was carefully controlled to keep the internal temperature below 75 °C. The reaction was allowed to proceed for 30 minutes, during which time the temperature naturally decreased to 60 °C. Samples were collected for NMR analysis, confirming partial consumption of the bis-silyl hydride and the formation of new Si-CH2 bonds.

[0136] Subsequently, trimethylvinylsilane (0.55 mol, 1.1 equivalent) was introduced dropwise at a controlled rate through a feeding funnel, ensuring the exothermic reaction did not exceed 75°C. After another 30 minutes, NMR analysis showed complete consumption of the bis-silyl hydride.

[0137] The reaction mixture was then vacuum distilled at 100°C for 1 hour under high vacuum (0 psi) to remove volatile components. The resulting product was used in coating formulations.

[0138] Step 3B: Synthesis of additives containing reactive trimethoxysilane and non-reactive aliphatic / aromatic olefin moieties

[0139]

[0140] The olefins used ( Representative list of )

[0141] , , , , ,as well as

[0142] Procedure: Accurately weigh 0.5 mol of PDMS di-hydride-1 (where the variable chain length n = 5 to 100) into a three-necked round-bottom flask (RB) equipped with a cooling water condenser, thermometer, and pressure-balanced feeding funnel. Purge the apparatus with nitrogen to establish an inert atmosphere. Then heat the reaction vessel to 60°C.

[0143] The Karstedt catalyst (2 ppm) was carefully added to a PDMS solution of bis-hydride-1, followed by thorough nitrogen purging. Trimethoxyvinylsilane (0.55 mol, 1.1 equivalents) was then introduced dropwise into the reaction mixture. An immediate exothermic reaction was observed, and the addition rate was carefully controlled to keep the internal temperature below 75 °C. The reaction was allowed to proceed for 30 minutes, during which time the temperature naturally decreased to 60 °C. Samples were collected for NMR analysis, confirming partial consumption of the bis-silyl hydride and the formation of new Si-CH2 bonds.

[0144] Subsequently, dodecene (0.55 mol, 1.1 equivalent) was introduced dropwise through a feeding funnel, followed by heating at 80 °C for 1 hour. NMR analysis indicated complete consumption of the bis-silyl hydride.

[0145] The reaction mixture was then vacuum distilled at 100°C for 1 hour under high vacuum (0 psi) to remove volatile components. The resulting product was used in coating formulations.

[0146] Example 2 - Synthesis of PDMS copolymer containing pendant hydrides

[0147] Step-1

[0148]

[0149] Procedure: Weigh 0.1 mol of HMMH into a three-necked round-bottom flask (RB) equipped with a cooling water condenser, thermometer, and pressure-balanced feeding funnel. Purge the apparatus with nitrogen to establish an inert atmosphere. Then heat the reaction vessel to 60°C.

[0150] The Karstedt catalyst (2 ppm) was carefully added to HMMH, followed by thorough nitrogen purging. Then, vinyltrimethylsilane (0.22 mol, 2.2 equivalents) was introduced dropwise into the reaction mixture. An exothermic reaction was immediately observed, and the addition rate was carefully controlled to keep the internal temperature below 75 °C. Vigorous reflux of vinyltrimethylsilane was observed. The reaction was allowed to continue for 1 hour, during which time the temperature naturally decreased to 60 °C. Samples were collected for NMR analysis, confirming the consumption of Si-H and the formation of two new Si-CH2 bonds, thereby forming MM. Then, the reaction mixture was vacuum distilled at 100°C for 1 hour under high vacuum (0 psi) to remove volatile components and unreacted vinyltrimethylsilane.

[0151] Step-2

[0152]

[0153] Procedure: Mix the compound MM (2g, 5.9mmol, 1 equivalent), D4 (7.08g, 23.89mmol, 4 equivalents), D4 (7.66 g, 11.94 mmol, 2 equivalents) and D4-H (1.43 g, 5.9 g, 1 equivalent) were placed in RB, and Amberlyst 15 (350 mg, ~2 wt%) catalyst was added under RT, and the mixture was stirred under RT for 8 hours. The solid content was then measured and showed to be 86%. The mixture was then vacuum distilled at 100 °C for 1 hour under high vacuum (0 psi) to remove volatile components and was used in the subsequent hydrosilylation reaction.

[0154] By changing MM according to the same procedure The loading amount is adjusted to obtain different chain lengths. Additionally, D4 and D4 are changed. The weight ratio of D4-H was used to synthesize different copolymers with different loadings of -Si(Me)3 and Si-H.

[0155] Step 3: Synthesis of additives containing reactive pendant trimethoxysilane and non-reactive terminal trimethylsilane

[0156]

[0157] Procedure: Weigh 0.1 mol of the suspended hydride into a three-necked round-bottom flask (RB) equipped with a cooling water condenser, thermometer, and pressure-balanced feeding funnel. Purge the apparatus with nitrogen to establish an inert atmosphere. Then heat the reaction vessel to 60°C.

[0158] The Karstedt catalyst (2 ppm) was carefully added, followed by thorough nitrogen purging. Trimethoxyvinylsilane (in excess) was then introduced dropwise into the reaction mixture. An exothermic reaction was immediately observed, and the addition rate was carefully controlled to keep the internal temperature below 75°C. The reaction was allowed to continue for 1 hour, during which time the temperature naturally decreased to 60°C. Samples were collected for NMR analysis, confirming that all Si-H bonds were consumed and two new Si-CH2 bonds were formed. The reaction mixture was then vacuum distilled at 100°C for 1 hour under high vacuum (0 psi) to remove volatile components and unreacted silane. It was then further used for coating applications.

Claims

1. Polysiloxane of formula (I): in, 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, R2, and R3 independently represent H, alkenyl, alkyl, cycloalkyl, aromatic group, heteroaromatic group, bicyclic group, -Si(OM)3, -CH2CH2Si(OM)3, -Si(Y)3, alkoxy, amino, epoxy, acrylate, hydroxyl, mercapto, carboxyl, or isocyanate. in, M is an alkyl group; Y is selected from alkyl, cycloalkyl, aromatic groups, heteroaromatic groups, bicyclic groups, and aliphatic fused rings; R4 is -CH3 or -C2H5; the condition is that when R2 and R3 are each -Si(CH3)3, then R4 is -CH2CH2Si(OCH3)3.

2. The polysiloxane of formula (I) according to claim 1, wherein, At least one of R1, R2 and R3 is a reactive group; or R2 and R3 are reactive groups; or at least one of R1, R2 and R3 is a trialkylsilane.

3. The polysiloxane of formula (I) according to claim 1, wherein, R4 is -CH2CH2Si(OCH3)3; and R2 and R3 are each -Si(CH3)3.

4. The polysiloxane of formula (I) according to claim 1, wherein, R4 is -CH2CH2Si(OCH3)3; R2 and R3 are each -Si(CH3)3; and R1 is -Si(Y)3.

5. Polysiloxanes of Formula (II): in, m = 1 to 100; n = 1 to 100; m+n = 5 to 100; m / n = 0.5 to 20; Q is selected from: , , , , , , , , , , ,as well as .

6. Polysiloxanes of Formula (III): in, m = 1 to 100; n = 1 to 100; m+n = 5 to 100; m / n = 0.5 to 20; Z is selected from: , , , , ,as well as .

7. A process for preparing formula (Ia), comprising reacting formula (IV) with trimethoxyvinylsilane in the presence of a Karstedt catalyst. in, m, n, and p are defined as above with respect to equation I.

8. A process for preparing 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... reaction, in, m, n, and Q are defined as described above with respect to Equation II.

9. A process for preparing 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... reaction, in, m, n, and Z are defined as described above with respect to Equation III.

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