Hydrosilane functionalization of [2.2]paracycl0phane to obtain, etch-resistant, stretchable and post-modifiable parylene

Abstract

The invention is based on a polymer, a process of manufacturing a polymer, as well as a polymer obtained by a process of manufacturing a polymer according to this invention. The invention also pertains to a surface-crosslinked polymer. Finally, the use of a polymer or a surface-crosslinked polymer according to this invention for coatings of electronics, medical instruments, implants, protection coatings for materials, coatings for glass, in the pharmaceutical industry, battery technology, construction chemistry, and aerospace applications, is also provided.

Description

[0001] HYDROSILANE FUNCTIONALIZATION OF [2.2]PARACYCL0PHANE TO OBTAIN, ETCHRESISTANT, STRETCHABLE AND POST-MODIFIABLE PARYLENE

[0002] FIELD OF THE INVENTION

[0003] [1] The invention is based on a polymer, a process of manufacturing a polymer, as well as a polymer obtained by a process of manufacturing a polymer according to this invention. The invention also pertains to a surface-crosslinked polymer. Finally, the use of a polymer or a surface-crosslinked polymer according to this invention for coatings of electronics, medical instruments, implants, protection coatings for materials, coatings for glass, in the pharmaceutical industry, battery technology, construction chemistry, and aerospace applications, is also provided.

[0004] DESCRIPTION

[0005] [2] Poly-para-xylenes, or so-called parylenes, have become a well-established polymer class in the conformal coating industry.

[0006] [3] Parylenes are semi-crystalline polymers and can be obtained through the chemical vapor deposition (CVD) of the corresponding functionalized or unfunctionalized [2.2]-para- cyclophane.M2]Here, the bridging carbon-carbon bond of the cyclophane gets cleaved at low pressures in the gas phase at temperatures above 500°C and in the so-called Gorham process.[3]After this cleavage, a chain growth polymerization occurs, and the parylene gets deposited in the cooled deposition chamber 'iii-H

[0007] [4] Due to their transparent nature, low electrical conductivity, and high biocompatibility, they are ideal candidates for coating medical devices and other delicate electronics. The properties of parylenes can be controlled through the functionalization of the dimer and the CVD method used.[5]Parylene C, which has one hydrogen atom in the aromatic chain substituted through a chlorine atom, is the most used parylene to this day[2L The chlorine functionalization makes the polymer more stable towards solvents and more durable under mechanical stress than its unfactionalized predecessor, parylene N. However, as for all parylenes, parylenes Cs mechanical properties depend strongly on the employed CVD setup. Also, a change in deposition temperature and pressure will lead to different crystallinity and crosslinking of the polymer, which radically changes the physical properties.[6]

[0008] [5] Polymers with higher crystallinity are generally more rigid than polymers with lower crystallinity. Crosslinked polymers are usually low in crystallinity since the crosslinking process does not allow for highly repetitive cell units. Nevertheless, with the additional internal bonding of crosslinked polymers, they can withstand higher mechanical stress while also having a higher stability towards solvents.

[0009] [6] Parylenes are usually obtained through low-pressure CVD systems, which is the most common and cheapest method available but only leads to linear parylenes with no crosslinking^]. A plasma-enhanced CVD system can be used to obtain crosslinked parylenes; however, they drive up the cost significantly.[8]A different way to crosslink parylenes is through the functionalization of the parylenes with hydroxy (parylene OH) or alkyl (parylene X) side chains. Here, the polymerization must first be carried out, followed by a treatment with light of a certain wavelength or a heat treatment to crosslink the polymer.1'’11101However, the additional step for crosslinking is not ideal, and in the case of untreated parylene OH, the resistance towards solvents, such as THF, is lost.[9]

[0010] [7] Sanzari et al. (I. Sanzari, M. Callisti, A. de Grazia, D. J. Evans, T. Polcar, T. Prodromakis, Scientific reports 2017, 7, 5764 =

[0011] ) show that Parylenes C can be treated post-polymerization to alter its wetting properties. Oxygen plasma can be applied to increase the hydrophilicity of the film by introducing hydrophilic groups to the films surface.

[0011] [8] Similar results have been obtained by M. Golda et al. (M. Golda, M. Brzychczy-Wloch, M. Faryna, K. Engvall, A. Kotarba, Materials science & engineering. C, Materials for biological applications 2.013, 33, 4221-4227 =

[0012] ). M. Golda et al. further demonstrate that this process damages the film by etching its surface. Importantly, the crosslinking of parylenes to enhance their durability is still challenging today, ad expensive setups need to be used to obtain crosslinked parylenes. Furthermore, the possibility of functionalization post-polymerization the polymerized parylene films is limited.

[0012] [9] Thus, there is still a need in the art for providing highly-crosslinked parylenes as well as films or other products thereof that are etch-resistant and chemically modifiable.

[0013]

[0010] All these problems are addressed with the first silicon hydride functionalized parylene SiH described in the present invention. In the present invention, the inventors present a straightforward and almost quantitative synthesis of the dimethyl hydrosilane functionalized 2.2- para-cyclophane, which can be used to obtain the corresponding parylene (parylene SiH). Through the formation of siloxane bonds in the gas phase during the low-pressure chemical vapor deposition (LP-CVD), crosslinking and internal bonding of the polymer generates paiylene SiH, which is a highly crosslinked, transparent, flexible, and etch-resistant polymer. The remaining Si- H bonds in the polymer allow for post-modification through oxygen plasma and various chemical oxidizing agents, which enhances stretchability while also increasing resistance to organic solvents. Every oxidation method alters the surface of the polymer in a different way, allowing for spot-on functionalization of the polymer to tailor the properties of the polymer postpolymerization. Moreover, through passivation of the surface under oxygen plasma, parylene SiH becomes practically etch-resistant.

[0014] BRIEF DESCRIPTION OF THE INVENTION

[0015]

[0011] Generally, and by way of brief description, the main aspects of the present invention can be described as follows:

[0012] In a first aspect, the invention pertains to a polymer comprising the structure according to the formula (I):

[0016]

[0013] In a second aspect, the invention pertains to a process of manufacturing a polymer, preferably a polymer according to the first aspect of this invention.

[0017]

[0014] In a third aspect, the invention pertains to a polymer obtained by a process according to the second aspect of this invention.

[0018]

[0015] In a fourth aspect, the invention pertains to a polymer having a structure according to any one of formula (II), formula (V), formula (VI), and / or formula (VII):

[0016] In a fifth aspect, the invention pertains to a surface crosslinked polymer, preferably a surface-crosslinked polymer obtained by a process according to the second aspect of this invention, comprising the structure according to the formula (VI) or the formula (VII):

[0019] (VID

[0020]

[0017] In a sixth aspect, the invention pertains to the use of a polymer according to the first or the fourth aspect of this invention, or a surface-crosslinked polymer according to the fifth aspect of this invention, for coatings of electronics, medical instruments, implants, protection coatings for materials, coatings for glass, in the pharmaceutical industry, battery technology, construction chemistiy, and aerospace applications.

[0021] DETAILED DESCRIPTION OF THE INVENTION

[0022]

[0018] In the following, the elements of the invention will be described. These elements are listed with specific embodiments, however, it should be understood that they may be combined in any manner and in any number to create additional embodiments. The variously described examples and preferred embodiments should not be construed to limit the present invention to only the explicitly described embodiments. This description should be understood to support and encompass embodiments which combine two or more of the explicitly described embodiments or which combine the one or more of the explicitly described embodiments with any number of the disclosed and / or preferred elements. Furthermore, any permutations and combinations of all described elements in this application should be considered disclosed by the description of the present application unless the context indicates otherwise.

[0023]

[0019] In a first aspect, the invention pertains to a polymer comprising the structure according to the formula (I): wherein Ri is selected from the group consisting of hydrogen, C1-C6 alkyl (preferably methyl), C1-C6 alkenyl, C1-C6 alkynyl, C3-C6 cycloalkyl (preferably phenyl), C3-C6 heterocyclyl, hydroxyl, hydroxymethyl, halogen, e. g. Cl or F, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e. g. OMe, or OCF3, and C1-C6 haloalkyl, e.g. CH2F, CHF2, CF3, CH2CF3, any of which is unsubstituted or substituted with one or several groups selected from halogen, e.g. Cl or F, C1-C6 alkyl, C1-C6 haloalkyl, e. g. CH2F, CHF2, CF3, CH2CF3, hydroxymethyl, hydroxyl, COOMe, C(O)H, COOH, alkoxy, in particular Ci- C3 alkoxy, e.g. OMe, or OCF3, and combinations thereof; wherein R2is selected from the group consisting of hydrogen, C1-C6 alkyl (preferably methyl), C1-C6 alkenyl, C1-C6 alkynyl, C3-C6 cycloalkyl (preferably phenyl), C3-C6 heterocyclyl, hydroxyl, hydroxymethyl, halogen, e. g. Cl or F, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e. g. OMe, or OCF3, and C1-C6 haloalkyl, e.g. CH2F, CHF2, CF3, CH2CF3, any of which is unsubstituted or substituted with one or several groups selected from halogen, e.g. Cl or F, C1-C6 alkyl, C1-C6 haloalkyl, e. g. CH2F, CHF2, CF3, CH2CF3, hydroxymethyl, hydroxyl, COOMe, C(O)H, COOH, alkoxy, in particular Ci- C3 alkoxy, e.g. OMe, or OCF3, and combinations thereof, and wherein R3is selected from the group consisting of hydrogen, C1-C6 alkyl (preferably methyl), C1-C6 alkenyl, C1-C6 alkynyl, C3-C6 cycloalkyl (preferably phenyl), C3-C6 heterocyclyl, hydroxyl, hydroxymethyl, halogen, e. g. Cl or F, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e. g. OMe, or OCF3, and C1-C6 haloalkyl, e.g. CH2F, CHF2, CF3, CH2CF3, any of which is unsubstituted or substituted with one or several groups selected from halogen, e.g. Cl or F, C1-C6 alkyl, C1-C6 haloalkyl, e. g. CH2F, CHF2, CF3, CH2CF3, hydroxymethyl, hydroxyl, COOMe, C(O)H, COOH, alkoxy, in particular Ci- C3 alkoxy, e.g. OMe, or OCF3, and combinations thereof.

[0020] According to the present invention, the term “polymer” refers to a substance or a material consisting of very large molecules linked together into chains of repeating subunits. Polymers, both natural and synthetic, are created via polymerization of many small molecules, known as monomers. Their consequently large molecular mass, relative to small molecule compounds, produces unique physical properties including toughness, high elasticity, viscoelasticity, and a tendency to form amorphous and semicrystalline structures rather than crystals. In one embodiment, the polymer is a polymer-coating, such as a post-modifiable polymer-coating. In one embodiment, the polymer is a synthetic plastic. The terms “polymer”, “polymer-coating” and “post-modifiable polymer-coating” can be used interchangeably. The “polymer”, “polymer- coating” and “post-modifiable polymer-coating” described herein can be used for a wide variety of applications, and are particularly interesting for a use in electronic applications, medical instruments, implants, protection coatings for materials, coatings for glass, in the pharmaceutical industry, battery technology, construction chemistry, and aerospace applications. In one embodiment, the polymer is a conductive material or a semi-conductive material. In one embodiment, the polymer is transparent, stretchable, flexible, soft, heat-resistant, etch-resistant, hydrophobic, and / or biocompatible. It is thus an advantage of the present invention to provide a polymer and a process for obtaining a polymer that is transparent, stretchable, flexible, soft, heat- resistant, etch-resistant, hydrophobic, and / or biocompatible. In one embodiment, which can be combined with each and every embodiment and aspect of the present invention, the polymer is a polymer film. In a preferred embodiment, the polymer is Parylene-SiH, which is transparent, stretchable, flexible, soft, heat-resistant, etch-resistant, hydrophobic, and / or biocompatible, and is thus an ideal candidate for very diverse technologies, such as for electronic applications, medical instruments, implants, protection coatings for materials, coatings for glass, in the pharmaceutical industry, battery technology, construction chemistry, and aerospace applications.

[0024]

[0021] According to the present invention, the terms “comprising” and “having”, such as “comprising the structure according to the formula (I)” and “having the structure according to the formula (I)” can be used interchangeably.

[0025]

[0022] According to the present invention, a polymer comprising the structure according to the formula (I)

[0026] CD can be referred to as Parylene SiRiR2R3

[0023] One embodiment relates to the polymer of the first aspect of this invention, wherein one of Ri, R2, and R3is hydrogen. In a further embodiment, the polymer comprises a structure according to the formula (X): wherein R is selected from the group consisting of hydrogen, C1-C6 alkyl (preferably methyl), Ci- C6 alkenyl, C1-C6 alkynyl, C3-C6 cycloalkyl (preferably phenyl), C3-C6 heterocyclyl, hydroxyl, hydroxymethyl, halogen, e. g. Cl or F, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e. g. OMe, or OCF3, and C1-C6 haloalkyl, e.g. CH2F, CHF2, CF3, CH2CF3, any of which is unsubstituted or substituted with one or several groups selected from halogen, e.g. Cl or F, C1-C6 alkyl, C1-C6 haloalkyl, e. g. CH2F, CHF2, CF3, CH2CF3, hydroxymethyl, hydroxyl, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e.g. OMe, or OCF3, and combinations thereof.

[0027]

[0024] One embodiment relates to the polymer of the first aspect of this invention, wherein Ri is hydrogen, R2is methyl and R3is methyl. In this embodiment, the polymer comprises the structure according to the formula (II):

[0028]

[0025] According to the present invention, a polymer comprising the structure according to the formula (II): can be referred to as Parylene SiH. The inventors surprisingly found a method for obtaining parylene SiH, which is described herein below. Moreover, the inventors surprisingly found that parylene SiH is highly advantageous, because it is a highly crosslinked, transparent, flexible, and etch-resistant polymer. The remaining SiH bonds in the polymer allow for post-modification through oxygen plasma and various chemical oxidizing agents. Every oxidation method alters the surface of the polymer in a different way, allowing for the highly advantageous spot-on functionalization of the polymer to tailor the properties of the polymer post-polymerization.

[0029]

[0026] In one embodiment, the polymer is a crosslinked, a transparent, a flexible, a stretchable, and / or an etch-resistant polymer, and / or wherein the polymer is modifiable post polymerization, such as modifiable through oxygen plasma and / or chemical oxidizing agents. In a further embodiment, a modification of the polymer post polymerization increases the resistance of the polymer to organic solvents. Importantly, every oxidation method alters the surface of the polymer in a different way, allowing for spot-on functionalization of the polymer to tailor the properties of the polymer post-polymerization. In one embodiment, the polymer is modifiable post polymerization by a spot-on functionalization.

[0030]

[0027] In a second aspect, the invention pertains to a process of manufacturing a polymer, preferably a polymer according to the first aspect of this invention, comprising the steps of:

[0031] (a) Providing paracyclophane, 4,i2-dibromo[2.2]paracyclophane and / or 4,12- diiodo[2.2]paracyclophane;

[0032] (b) Optionally, treating paracyclophane with Br2and / or I2, thereby obtaining 4,12- dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane;

[0033] (c) Functionalizing 4,i2-dibromo[2.2]paracyclophane and / or 4,12- diiodo[2.2]paracyclophane, wherein the functionalizing comprises the step of treating 4,i2-dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane with t-BuLi, n-BuLi, SiClRiR2R3, HSiClR2R3, and / or HSiClMe2, in a solvent, such as Tetrahydrofuran (THF), Diethyl ether, Hexane, Pentane, Toluol, or a solvent mixture thereof, thereby obtaining a dimer according to formula (III);

[0034] (d) Purifying the dimer obtained in step (c), such as purifying the dimer obtained in step (c) by sublimating the dimer, wherein the sublimating preferably occurs at a temperature range and / or a pressure range, preferably wherein the temperature range is between i6o°C and 200°C, more preferably between 165°C and i8o°C, and / or preferably wherein the pressure range is preferably between 0.02 and 0.10 mbar, more preferably around 0.04 mbar, thereby obtaining a purified dimer according to formula (III); (e) Polymerizing the purified dimer obtained in step (d), such as by chemical vapor deposition, thereby obtaining a polymer, and

[0035] (f) Optionally, additional surface-crosslinking of the polymer as obtained in step (e), preferably wherein said surface-crosslinking is achieved by oxygen plasma treatment, H202(aq.), NaOCl (aq.), and / or KMnO4(aq.), thereby obtaining a surface-crosslinked polymer.

[0036]

[0028] The inventors surprisingly found a straightforward and almost quantitative synthesis method of the dimethyl hydrosilane functionalized 2.2-para-cyclophane, which can be used to obtain the corresponding parylene (such as paiylene SiH). Through the formation of siloxane bonds in the gas phase during the chemical vapor deposition, crosslinking of the polymer and internal bonding through the formation of siloxane bonds generates parylene SiH, which is a highly crosslinked, transparent, flexible, and etch-resistant polymer.

[0037]

[0029] Of note, 4,i2-dibromo[2.2]paracyclophane has the following structure:

[0038]

[0030] According to the present invention, a dimer according to formula (III) can be referred to as cyclophane SiRiR2R3.

[0039]

[0031] In one embodiment, the dimer according to formula (III) obtained in step c) is characterized in that one of Rx, R2, and R3is hydrogen.

[0040]

[0032] In one embodiment, the dimer according to formula (III) obtained in step c) is characterized in that Ri is hydrogen, R2is methyl and R3is methyl. In this embodiment, the dimer comprises the structure according to the formula (IV):

[0033] The silicon hydride functionalized parylene SiH thereby obtained is highly advantageous, because it is a highly crosslinked, transparent, flexible, and etch-resistant polymer. The remaining Si-H bonds in the polymer allow for post-modification through oxygen plasma and various chemical oxidizing agents, which enhances stretchability while also increasing resistance to organic solvents. Every oxidation method alters the surface of the polymer in a different way, allowing for spot-on functionalization of the polymer to tailor the properties of the polymer postpolymerization. Moreover, through passivation of the surface under oxygen plasma, parylene SiH is practically etch-resistant.

[0041]

[0034] In one embodiment, polymerizing the purified dimer in step (e) of the method occurs by chemical vapor deposition, thereby obtaining a polymer.

[0042]

[0035] In a further preferred embodiment, polymerizing the purified dimer in step (e) of the method occurs by chemical vapor deposition according to the following reaction:

[0043] Parylene SiH

[0044]

[0036] In one embodiment, polymerizing the purified dimer in step (e) of the method occurs by chemical vapor deposition (CVD), wherein the CVD comprises the following steps:

[0045] (i) Sublimating the dimer according to formula (III) obtained in step c) of the method according to the second aspect of this invention, wherein the sublimating preferably occurs at a temperature range of between 17O°C to 200°C, thereby obtaining a sublimated dimer;

[0046] (ii) Pyrolyzing the sublimated dimer obtained in step (i), wherein the pyrolyzing preferably occurs at a temperature range of between 6io°C to 7OO°C, thereby obtaining a pyrolyzed dimer, and

[0047] (iii) Depositing the pyrolyzed dimer, wherein the depositing preferably occurs at a temperature range of between 20°C to 4O°C.

[0048]

[0037] According to one embodiment, the air pressure during the polymerizing reaction of the purified dimer in step (e) of the method by chemical vapor deposition (CVD) is between 1-ioPa. Thus, during any of the steps of sublimating according to (i), pyrolyzing according to (ii) and depositing according to (iii), the air pressure is between 1-ioPa.

[0038] The inventors surprisingly found that after the step (e) of polymerizing the purified dimer obtained by chemical vapor deposition, the thereby obtained polymer is already crosslinked to a certain amount, and / or oxygen is already incorporated into the polymer. The inventors thus demonstrated that parylene SiH can crosslink itself during the polymerization, which is an unseen property for LP-CVD deposited parylenes. In one embodiment, the polymer according to the present invention can crosslink itself.

[0049]

[0039] Importantly, additional surface-crosslinking of the polymer according to step (f) further enhances the amount of crosslinking within the polymer. Moreover, the inventors surprisingly found that when Parylene SiH is treated with oxygen post-polymerization, oxygen is incorporated into every single bond of the silicon. In one embodiment, when Parylene SiH is treated with oxygen post-polymerization, oxygen is incorporated into almost every or every single bond of the silicon.

[0050]

[0040] Importantly, the inventors found that the remaining Si-H bonds in the polymer allow for post-modification through oxygen plasma and various chemical oxidizing agents, which enhances stretchability while also increasing resistance to organic solvents. Thus, the Si-H group is important for the additional surface-crosslinking of the polymer, preferably wherein said surfacecrosslinking is achieved by oxygen plasma treatment, in step (f) of the method.

[0051]

[0041] Importantly, the reaction from Si-H to Si-O-Si is a highly favoured reaction for 4,16- bis(dimethylsilyl)[2.2]paracyclophane, as can be seen in Figure 2.

[0052]

[0042] The inventors surprisingly found that with the synthesis procedure of the precursor 4,16- bis(dimethylsilyl)[2.2]paracyclophane presented here, the corresponding parylene SiH can be obtained in high quantities and quality through low-pressure chemical vapor deposition. Furthermore, it was shown that parylene SiH is highly crosslinked after the CVD, which is an unseen property for LP-CVD deposited polymers. The softness of and durability of parylene SiH in its unmodified form make it an ideal candidate for the coating of delicate and flexible materials. Through the various ways to additionally post-modify parylene SiH, this work shows what a powerful tool the dimethyl silicon hydride functionalization of organic polymers can be. For example, through the oxidation of the Si-H bonds post-polymerization, the stretchability of the parylene can be enhanced significantly. The hydrosilane functionalization makes the polymer practically etch-resistant which is a unique feature of parylene SiH. This invention displays outstanding properties of parylene SiH obtained with a cheap and accessible method.

[0053]

[0043] Importantly, the trans-configuration of the two silicon (hydride) containing substituents in the dimer has an unexpected effect. Importantly, the trans-configuration of the two silicon (hydride) containing substituents can be synthesized almost quantitatively out of the trans-bromo dimer. It also has an ideal sublimation temperature for chemical vapor deposition (CVD).

[0054]

[0044] In one embodiment, if the dimer obtained in step c) has the following structure according to the formula (XI): a preferred process is:

[0055]

[0045] In one embodiment, the step of treating paracyclophane with Br2and / or I2, thereby obtaining 4,i2-dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane, according to step (b) of the method has a yield of around 25% to 50%, preferably of 30% to 35%.

[0056]

[0046] In one embodiment, the step of functionalizing 4,i2-dibromo[2.2]paracyclophane and / or

[0057] 4,i2-diiodo[2.2]paracyclophane according to step (c) of the method has a yield of at least 90%, preferably of at least 95%, more preferably of around 98%.

[0058]

[0047] According to the present invention, the term “sublimating” refers to a method of purification, wherein a solvent or a solvent mixture is evaporated.

[0059]

[0048] One embodiment relates to the process of manufacturing according to the second aspect of this invention, wherein the treating in step b) comprises a treatment duration of between 3 and 5 hours, optionally wherein the treating in step b) occurs at a temperature range of between 55°C and 75°C, and / or wherein the stoichiometric ratio of paracyclophane to Br2is between 1.0 to 6.0 and 1.0 to 6.5, further optionally wherein the treating in step b) occurs in presence of CHC13.

[0060]

[0049] One embodiment relates to the process of manufacturing according to the second aspect of this invention, wherein the functionalizing in step (c) comprises:

[0061] (i) Suspending 4,i2-dibromo[2.2]paracyclophane and / or 4,12- diiodo[2.2]paracyclophane in a solvent, such as Tetrahydrofuran (THF), Diethyl ether, Hexane, Pentane, Toluol, or a solvent mixture thereof, thereby obtaining a suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,12- diiodo[2.2]paracyclophane;

[0062] (ii) Adding t-BuLi to the suspension comprising 4,i2-dibromo[2.2]paracyclophane or

[0063] 4.12-diiodo[2.2]paracyclophane obtained in step (i) at a first temperature range and stirring for a first time period to obtain a first mixture, wherein the first temperature range is between -78°C and -65°C, preferably wherein the stoichiometric ratio of

[0064] 4.12-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane to t-BuLi is between 1.0 to 4.0 and 1.0 to 4.5, more preferably wherein the stoichiometric ratio of 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane to t-BuLi is around i.o to 4.1, optionally wherein the molarity of t-BuLi is around 1.6 M;

[0065] (iii) Stirring the first mixture for 10 to 60 minutes, preferably for 15 minutes, at a second temperature range, wherein the second temperature range is between -io°C to 5°C, preferably around o°C;

[0066] (iv) Adding SiClRiR2R3, HSiClR2R3, and / or HSiClMe2, to the first mixture obtained in step (iii) at a third temperature range to obtain a second mixture, wherein the third temperature range is between -78°C and -65°C, wherein the stoichiometric ratio of SiClRiR2R3, HSiClR2R3, and / or HSiClMe2to 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane is between 1.0 to 4.0 and 1.0 to 4.5, more preferably wherein the stoichiometric ratio is around 1.0 to 4.1, thereby obtaining a third mixture;

[0067] (v) Stirring the third mixture at a fourth temperature range, wherein the fourth temperature range is between 20°C and 30°C, optionally wherein the time period of the stirring is between 16 and 24 hours;

[0068] (vi) Optionally, removing the solvent from the third mixture to obtain a product, and

[0069] (vii) Further optionally, purifying the product, such as purifying the product by sublimating the product.

[0070]

[0050] In a preferred embodiment, the suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane obtained in step (i) is cooled down to a first temperature range, wherein the first temperature range is between -78°C and -65°C, preferably around -70°C. After cooling down to the first temperature range, t-BuLi is added to the suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane. After full addition of t- BuLi, the suspension is stirred for a first time period, wherein the first time period is between 30 min and 3 hours, preferably around 45mm, at the first temperature range, wherein the first temperature range is between -78°C and -65°C, preferably around -70°C.

[0071]

[0051] In a further preferred embodiment, the first mixture is cooled down to a third temperature range, wherein the third temperature range is between -78°C and -65°C, preferably around -70°C, before addition of SiClRiR2R3, HSiClR2R3, and / or HSiClMe2in step (iv) of the method. The third mixture is then stirred at a fourth temperature range, wherein the fourth temperature range is between 20°C and 30°C, optionally wherein the time period of the stirring is between 16 and 24 hours. In a preferred embodiment, the fourth temperature range is achieved by removing the cooling, causing the solutions to warm up again.

[0072]

[0052] In one embodiment, the solvent is removed from the third mixture to obtain a product in step (vi) of the method. In a further embodiment, the solvent is removed from the third mixture to obtain a product in step (vi) of the method under vacuum.

[0053] One embodiment relates to the process of manufacturing according to the second aspect of this invention, wherein the functionalizing in step (c) comprises:

[0073] (i) Suspending 4,i2-dibromo[2.2]paracyclophane and / or 4,12- diiodo[2.2]paracyclophane in a solvent, such as Tetrahydrofuran (THF), Diethyl ether, Hexane, Pentane, Toluol, or a solvent mixture thereof, thereby obtaining a suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,12- diiodo[2.2]paracyclophane;

[0074] (ii) Adding n-BuLi to the suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane obtained in step (i) at a first temperature range, wherein the first temperature range is between -78°C and -65°C, optionally wherein the stoichiometric ratio of 4,i2-dibromo[2.2]paracyclophane or 4,12- diiodo[2.2]paracyclophane to n-BuLi is between i.o to 6.0 and i.o to 8.0, preferably wherein the stoichiometric ratio of 4,i2-dibromo[2.2]paracyclophane or 4,12- diiodo[2.2]paracyclophane to n-BuLi is around 1.0 to 8.0, further optionally wherein the molarity of n-BuLi is around 1.6 M;

[0075] (iii) Stirring the first mixture for 1 to 3 hours at a second temperature range, wherein the second temperature range is between 30°C to -40°C;

[0076] (iv) Adding SiClRiR2R3, HSiClR2R3, and / or HSiClMe2, to the first mixture obtained in step (iii) at a third temperature range to obtain a second mixture, wherein the third temperature range is between -78°C and -65°C, wherein the stoichiometric ratio of SiClRiR2R3, HSiClR2R3, and / or HSiClMe2to 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane is between 1.0 to 6.0 and 1.0 to 8.0, more preferably wherein the stoichiometric ratio is around 1.0 to 4.1, thereby obtaining a third mixture;

[0077] (v) Stirring the third mixture at a fourth temperature range, wherein the fourth temperature range is between 20°C and 30°C, for 16 to 24 hours;

[0078] (vi) Optionally, removing the solvent from the third mixture to obtain a product, and

[0079] (vii) Further optionally, purifying the product, such as purifying the product by sublimating the product.

[0080]

[0054] In a preferred embodiment, the suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane obtained in step (i) is cooled down to a first temperature range, wherein the first temperature range is between -78°C and -65°C, preferably around -70°C. After cooling down to the first temperature range, n-BuLi is added to the suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane. After full addition of n- BuLi, the suspension is stirred for a first time period, wherein the first time period is between 30 min and 3 hours, preferably around 45mm, at the first temperature range, wherein the first temperature range is between -78°C and -65°C, preferably around -70°C.

[0055] In a further preferred embodiment, the first mixture is cooled down to a third temperature range, wherein the third temperature range is between -78°C and -65°C, preferably around -70°C, before addition of SiClRiR2R3, HSiClR2R3, and / or HSiClMe2in step (iv) of the method. The third mixture is then stirred at a fourth temperature range, wherein the fourth temperature range is between 20°C and 30°C, optionally wherein the time period of the stirring is between 16 and 24 hours. In a preferred embodiment, the fourth temperature range is achieved by removing the cooling, causing the solutions to warm up again.

[0081]

[0056] In one embodiment, the solvent is removed from the third mixture to obtain a product in step (vi) of the method. In a further embodiment, the solvent is removed from the third mixture to obtain a product in step (vi) of the method under vacuum.

[0082]

[0057] According to the present invention, each reaction step of the method according to the present invention except of the step of

[0083] (b) Optionally, treating paracyclophane with Br2 and / or I2, thereby obtaining 4,12- dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane is conducted under argon or nitrogen atmosphere. Moreover, according to the present invention, each reaction step of the method according to the present invention except of the step of

[0084] (b) Optionally, treating paracyclophane with Br2 and / or I2, thereby obtaining 4,12- dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane is conducted with dry solvents.

[0085]

[0058] In one embodiment, each reaction step of the method according to the present invention except of the step of

[0086] (b) Optionally, treating paracyclophane with Br2 and / or I2, thereby obtaining 4,12- dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane is conducted under argon or nitrogen atmosphere.

[0087]

[0059] In one embodiment, each reaction step of the method according to the present invention except of the step of

[0088] (b) Optionally, treating paracyclophane with Br2 and / or I2, thereby obtaining 4,12- dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane is conducted with dry solvents.

[0089]

[0060] In one embodiment, the optional step of treating paracyclophane with Br2 and / or I2, thereby obtaining 4,i2-dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane is conducted under air.

[0090]

[0061] According to the present invention, the terms „dissolving“ and „suspending“ can be used interchangeably. Similarly, the terms „solution“, “dispension” and „suspension“ can be used interchangeably. In one embodiment, 150 mL of a solvent are added per 4 grams of 4,12- dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane. This does not result in a fully dissolved solution, but instead a dispension or a suspension comprising 4,12- dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane. However, as the person of skill is well aware, whether a „solution“, “dispension” or a „suspension“ is obtained is dependent on the amount of solvent added.

[0091]

[0062] In one embodiment, the solvent used in step (i) of the method is Tetrahydrofuran (THF). In one embodiment, the amount of THF used does not dissolve the full amount of paracyclophane. Therefore, after the addition of THF, we obtain a suspension of the paracyclophane and THF.

[0092]

[0063] In one embodiment, for the step of suspending according to step (i), no specific time for stirring is needed, and the next reaction step can be started immediately with the suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane obtained.

[0093]

[0064] In one embodiment, which can be combined with each embodiment and aspect of the present invention, the equivalents of t-BuLi or n-BuLi as added to the suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane in step (ii) of the method must be matched. As an example, if 4.0 eq t-BuLi is used, 4.0 eq of SiClRiR2R3, HSiClR2R3, and / or HSiClMe2must also be used. If 4.5 eq t-BuLi is used, 4.5 eq of SiClRiR2R3, HSiClR2R3, and / or HSiClMe2must also be used.

[0094]

[0065] In one embodiment, the dimer obtained in step c) is 4,16- bis(dimethylsilyl)[2.2]paracyclophane having a structure according to formula (IV):

[0095]

[0066] One embodiment relates to the process of manufacturing according to the second aspect of this invention, wherein the polymer as obtained in step (e) comprises a mixture of a polymer comprising the structure according to the formula (II) and a polymer comprising the structure according to the formula (VI):

[0096]

[0067] According to the present invention, the terms “polymer”, “crosslinked polymer” and “surface-crosslinked polymer” can be used interchangeably. In some embodiments, the terms “polymer”, “crosslinked polymer” and “surface-crosslinked polymer” can be used for a parylene, such as a surface-crosslinked parylene. In a preferred embodiment, the polymer is a parylene. In a further preferred embodiment, the polymer is a surface-crosslinked parylene.

[0097]

[0068] One embodiment relates to the process of manufacturing according to the second aspect of this invention, wherein the surface-crosslinked polymer obtained in step f) has a structure according to the formula (VII), optionally wherein a further product obtained in step f) is a polymer comprising a structure according to the formula (V): optionally

[0069] According to the present invention, the further product obtained in step f) can be a compound, a polymer, and / or a parylene.

[0098]

[0070] According to the present invention, a polymer comprising a structure according to the formula (V) can be referred to as Si-OH Parylene.

[0099]

[0071] One embodiment relates to the process of manufacturing according to the second aspect of this invention, wherein the yield of the surface-crosslinked polymer as obtained in step (f) of the method depends on the treatment time, the treatment agent, and / or the amount of functionalizing as performed in step (c), and wherein the crosslinking depends on the amount of oxygen present in the chemical vapor deposition.

[0100]

[0072] One embodiment relates to the process of manufacturing according to the second aspect of this invention, wherein the additional surface-crosslinking in step (f) enhances the molecular mass of the polymer, optionally wherein the higher molecular mass of the surface-crosslinked polymer enhances the stability of the surface-crosslinked polymer towards a solvent, increases the hydrophobicity of the polymer, and / or alters the mechanical properties of the of the polymer.

[0101]

[0073] Accordingly, the additional surface-crosslinking in step (f) is a way to change the mechanical properties of the polymer post-deposition. It is thus an advantage of the present invention that the polymer of this invention and the polymer obtained by a process of manufacturing according to this invention is a post-modifiable polymer and / or a post-modifiable polymer coating.

[0102]

[0074] In a third aspect, the invention pertains to a polymer obtained by a process according to the second aspect of this invention.

[0103]

[0075] In one embodiment, the polymer according to the third aspect of this invention has a structure according to any one of formula (II), formula (V), formula (VI), and / or formula (VII):

[0104]

[0076] In one embodiment, the adhesive properties of parylene SiH is enhanced compared to other parylenes, such as regular parylene. In one embodiment, the adhesive properties of parylene SiH is enhanced compared to other parylenes, because the silane sidechain also enhances the adhesion to surfaces compared to regular parylene.

[0105]

[0077] In a fourth aspect, the invention pertains to a polymer having a structure according to any one of formula (II), formula (V), formula (VI), and / or formula (VII):

[0106] (ID (V)

[0107]

[0108]

[0078] In a fifth aspect, the invention pertains to a surface-crosslinked polymer, preferably a surface-crosslinked polymer obtained by a process according to the second aspect of this invention, comprising the structure according to the formula (VI) or the formula (VII):

[0079] In one embodiment, the surfaces of a polymer and / or a surface-crosslinked polymer according to the present invention are connected by Si-O-Si bonds.

[0109]

[0080] In a sixth aspect, the invention pertains to the use of a polymer according to the first or the fourth aspect of this invention, or a surface-crosslinked polymer according to the fifth aspect of this invention, for coatings of electronics, medical instruments, implants, protection coatings for materials, coatings for glass, in the pharmaceutical industry, battery technology, construction chemistry, and aerospace applications.

[0110]

[0081] The terms “of the [present] invention”, “in accordance with the invention”, “according to the invention” and the like, as used herein are intended to refer to all aspects and embodiments of the invention described and / or claimed herein.

[0111]

[0082] As used herein, the term “comprising” is to be construed as encompassing both “including” and “consisting of’, both meanings being specifically intended, and hence individually disclosed embodiments in accordance with the present invention. Where used herein, “and / or” is to be taken as specific disclosure of each of the two specified features or components with or without the other. For example, “A and / or B” is to be taken as specific disclosure of each of (i) A, (ii) B and (iii) A and B, just as if each is set out individually herein. In the context of the present invention, the terms “about” and “approximately” denote an interval of accuracy that the person skilled in the art will understand to still ensure the technical effect of the feature in question. The term typically indicates deviation from the indicated numerical value by ±20%, ±15%, ±10%, and for example ±5%. As will be appreciated by the person of ordinary skill, the specific such deviation for a numerical value for a given technical effect will depend on the nature of the technical effect. For example, a natural or biological technical effect may generally have a larger such deviation than one for a man-made or engineering technical effect. As will be appreciated by the person of ordinary skill, the specific such deviation for a numerical value for a given technical effect will depend on the nature of the technical effect. For example, a natural or biological technical effect may generally have a larger such deviation than one for a man-made or engineering technical effect. Where an indefinite or definite article is used when referring to a singular noun, e.g. "a", "an" or "the", this includes a plural of that noun unless something else is specifically stated.

[0112]

[0083] It is to be understood that application of the teachings of the present invention to a specific problem or environment, and the inclusion of variations of the present invention or additional features thereto (such as further aspects and embodiments), will be within the capabilities of one having ordinary skill in the art in light of the teachings contained herein.

[0113]

[0084] Unless context dictates otherwise, the descriptions and definitions of the features set out above are not limited to any particular aspect or embodiment of the invention and apply equally to all aspects and embodiments which are described.

[0114]

[0085] All references, patents, and publications cited herein are hereby incorporated by reference in their entirety. BRIEF DESCRIPTION OF THE FIGURES

[0115]

[0086] The figures show:

[0116]

[0087] Figure 1 shows a) the synthesis procedure to obtain precursor 4,16- bis(dimethylsilyl)[2.2]paracyclophane (1). b) schematic representation of the CVD polymerization process of parylene SiH. c) FTIR spectrum of Parylene SiH film with clear Si-H stretching at 2114 cm1, d)29Si NMR (INEPT) of Parylene SiH recorded in CeDe. e) ‘H NMR of Parylene SiH recorded in CeDe. f) XPS spectrum of parylene SiH. g) Schematic representation of analyses performed for certain thicknesses.

[0117]

[0088] Figure 2 shows DFT-calculated free energy reaction coordinate of the proposed mechanism of the formation of diphenoxydisiloxane bridging unit between two phenyl moieties from dimethyl(phenyl)silane in the presence of oxygen under elimination of water, at the PBEo- D4 / def2-TZVP / / PBEo-D4 / def2-TZVP level of theory (at 298.15 K).

[0118]

[0089] Figure 3 shows a) XPS spectra of Si 2p orbital of untreated Parylene SiH (top), 1 min oxygen plasma treated Parylene SiH (second from top), 5 min oxygen plasma treated Parylene SiH (third from top), 10 min oxygen plasma treated Parylene SiH (bottom), b) XPS spectra displaying the change of parylene SiHs surface composition when treated with different aquatic oxidizing agents: untreated Parylene SiH (top), KMnO4treated Parylene SiH (second from top), H2O2 treated Parylene SiH (third from top), NaOCl treated Parylene SiH (bottom), c) FTIR- spectrum of Parylene SiH film with oxygen-plasma treatment from 1 to 10 minutes. The integral in the Si-O-Si vibration region is highlighted, showcasing Si-O-Si formation, d) FTIR spectrum of parylene SiH when treated with aquatic oxidizing agents, e) Comparison of O2 plasma etching behavior of Parylene SiH and Parylene C. f) AFM images of untreated, 1 min 02plasma treated, 5 min 02plasma treated and 10 min 02plasma treated Parylene SiH, deposited on a silicon wafer, g) Tensile testing of different parylene SiHs (Parylene SiH untreated, 1 min 02plasma treated and NaOCl (aq.)), parylene C and parylene TMS, showcasing flexibility and impact of oxygen treatment, h) Setup for oxygen plasma treatment, i) comparison of solubility of untreated parylene SiH (left) and one-minute oxygen plasma treated parylene SiH (right), j) Thermogravimetric analysis (TGA) showcasing similar thermal stability of Parylene SiH and Parylene-C. No significant change between 1 to 10 minutes of oxygen plasma treatment can be observed, k) Main polymer structure of parylene SiH and parylene TMS and a schematic representation of their stretchability

[0119]

[0090] Figure 4 a) shows a comparison of ‘H NMR spectra of 4,16- bis(dimethylsilyl)[2.2]paracyclophane (1) and 4,i2-bis(dimethylsilyl)[2.2]paracyclophane (2). b)13C NMR spectrum of 4,i6-bis(dimethylsilyl)[2.2]paracyclophane (1). c)29Si-NMR of 4,16- bis(dimethylsilyl)[2.2]paracyclophane, proofing the successful synthesis of the dimer by showing the expected product peak, d) 'H-NMR of 4,i6-bis(dimethylsilyl)[2.2]paracyclophane, proofing the successful synthesis of the dimer by showing the expected product peaks, e) shows the crystal structure of 4,i6-bis(dimethylsilyl)[2.2]paracyclophane obtained by single crystal X-ray diffraction at 100K.

[0120]

[0091] Figure 5 shows that UV-Vis of Parylene SiH film shows full transparency in the visible region.

[0121]

[0092] Figure 6 shows the comparison of impedance of Parylene C and Parylene SiH.

[0122]

[0093] Figure 7 shows a) Schematic representation of formation of passivated surface of parylene SiH in an oxygen plasma chamber, b) full XPS spectra of untreated parylene SiH and parylene SiH treated for 1, 5 and 10 minutes with oxygen plasma.

[0123]

[0094] Figure 8 shows a process according to one embodiment of the present invention.

[0124] EXAMPLES

[0125]

[0095] Certain aspects and embodiments of the invention will now be illustrated by way of example and with reference to the description, figures and tables set out herein. Such examples of the methods, uses and other aspects of the present invention are representative only, and should not be taken to limit the scope of the present invention to only such representative examples.

[0126]

[0096] The examples show:

[0127] Example 1: Synthsis of 4,i6-bis(dimethylsilyl)[2.2]paracyclophane (1)

[0128]

[0097] 4-0 g (10.93 mmol, 1.0 eq.) of dibromo[2.2]paracylophane was dissolved in 150 mL THF. After cooling the solution to -76 °C, 26.4 mL (44.80 mmol, 4.1 eq.) of a 1.7 molar solution of t- BuLi were added over the course of 15 minutes. The reaction mixture was stirred for 45 min at - 76 °C and then warmed up to o °C. After reaching o °C, the reaction mixture was cooled back down again to -76 °C, and 4.9 mL (44.80 mmol, 4.1 eq.) dimethylchlorosilane were added slowly. The reaction mixture was stirred for 16 h and allowed to warm up to room temperature during that time. After removal of the solvent and subsequent sublimation at 175 °C at 0.04 mbar the product was obtained as colorless powder in 98 % yield.

[0129]

[0098] mp 124,1 °C; ‘H NMR (400 MHz, CeDr,) 8 (ppm) = 6.73 (d, J = 1.9 Hz, 2H), 6.59 (dd, J = 7.8, 1.9 Hz, 2H), 6.26 (d, J = 7.7 Hz, 2H), 4.78 (hept, J = 3.7 Hz, 2H), 3.29 (ddd, J = 12.6, 10.5, 3.0 Hz, 2H), 3.16 - 3.01 (m, 2H), 2.98 - 2.77 (m, 4H), 0.37 (d, J = 3.8 Hz, 6H), 0.23 (d, J = 3.7 Hz, 6H);J3C NMR (101 MHz, CeDr,) 8 (ppm) = 145.77 (s), 138.05 (s), 137.93 (s), 137.08 (s), 133.72 (s), 133.23 (s), 35.04 (d, J = 44.1 Hz), -3.53 (d, J = 170.1 Hz);2<)Si NMR (80 MHz, CeDr,) 8 (ppm) = -21.30 (s); Anal, calcd for C2oH28Si2: C 74.00, H 8.69, found: C 73.97, H 8.58

[0130] Example 2: Synthesis and characterization of hydrosilane functionalized parylene

[0131]

[0099] Starting from the 4,i6-dibromo[2.2]paracyclophane, the precursor for parylene SiH, 4,16- bis(dimethylsilyl)[2.2]paracyclophane (1), can be obtained almost quantitatively by the reaction shown in Figure la, which is conducted under argon atmosphere. After lithiation and the addition of dimethyl chlorosilane, the product can be purified by sublimation under argon atmosphere at 17O°C at a pressure of 0,04 mbar. The sublimation at higher temperatures and higher pressures lead to a mixture of the trans and 4,i2-bis(dimethylsilyl)[2.2]paracyclophane (2), which does not affect the later-on CVD process, but it lowers the yield of the overall reaction and increases the complexity of the recorded NMR spectra. For this reason, the sublimation temperature was held below i8o°C to ensure a 98% conversion to 4,i6-bis(dimethylsilyl)[2.2]paracyclophane (1). The successful synthesis of the enantiomer pure 4,i6-bis(dimethylsilyl)[2.2]paracyclophane was proven by NMR, MS, EA, and SC-XRD.

[0132]

[0100] To obtain NMR spectra a Bruker Avance Neo 400 MHz or n Bruker Avance Neo 400 MHz or a Avance 500 MHz spectrometer was used. The evaluation of the spectra was performed using MestReNova (version 15.0.0) from Mestrelab Reasearch S.L. The following abbreviations were used for the different multiplicities of NMR spectra obtained: s = singlet, d = doublet, t = triplet and m = multiplet.

[0133]

[0101] All mass spectra were recorded on an Exactive Plus Orbitrap system by Thermo Fischer Scientific from LINDEN CMS GmbH. The ionization was carried out via a liquid injection field desorption ionization (LIFDI) source. The samples were prepared in toluene under the exclusion of air followed by the under-argon atmosphere.

[0134]

[0102] For the CVD of 4,i6-bis(dimethylsilyl)[2.2]paracyclophane (1), the same temperature program as that of parylene C was used to compare the polymer properties of both parylenes under the same CVD conditions.

[0135]

[0103] Every polymerization proceeded through the following steps: sublimation at 170 °C, pyrolysis in the oven at 690 °C, and finally, deposition on a glass or silicon wafer at room temperature (Figure ib). The pressure through the hole process was kept at around 0.04 mbar. Per used gram of 4,i6-bis(dimethylsilyl)[2.2]paracyclophane (1), a thickness of roughly 0.8 pm parylene SiH could be achieved.

[0136]

[0104] Since the parylene SiH is flexible and durable, films thinner than 1 pm can already be handled nicely for testing. However, to minimize the error of the thickness measurement and further facilitate the handling, polymer films of a thickness between 2.0 and 2.5 pm were produced and tested.

[0137]

[0105] Parylene SiH is a transparent, colorless, and flexible polymer. Through FTIR, the intactness of the integrated SiMe2H group was confirmed. The stretching vibration of the Si-H bond can be observed at 2116 cm1, while the vibrations at 1247.8 and 874.6 cm1can be attributed to the Si-Me bonds as seen in Figure ic. Of note, with FTIR, certain bonds can be detected by letting them vibrate and see at what frequency the vibrations occur. These vibrations are in good agreement with the wave numbers given in the literature. All further signals can be attributed to the poly-para-xylene vibrations.

[0138]

[0106] The performed X-ray photoelectron spectrum (XPS) reveals that two different silicone species are present on the surface of parylene SiH. The binding energy of 100.9 eV corresponds to the unoxidized silane group of the polymer, and the binding energy of 101.8 eV to the twice oxidized version 02SiMe2. These values agree with the binding energies of silanes and dimethyl siloxanes of similar structures given in the literature. Since 4,16- bis(dimethylsilyl)[2.2]paracyclophane (1), the precursor of parylene SiH, does not contain oxygen; the siloxane groups must form during the CVD with the remaining oxygen in the system at 0.04 mbar of air pressure. Furthermore, since the siloxanes formed and are twice oxidized, the crosslinking of two in proximity laying Si-H groups is not only possible but probable since H20 can be cleaved off in a condensation reaction and removed in the process, which increases entropy. These cross-linked siloxane species can also be observed in the recorded LIFDI-MS.

[0139]

[0107] These hydrosilane and siloxane groups were further confirmed by the recorded 298! NMR spectrum seen in Figure id. Here, the signal at -21.0 ppm and -21.4 ppm can be attributed to the unoxidized hydrosilane. One signal originates from head-to-tail and one from head-to-head polymerization, as seen in Figure id. The 298! NMR signal with negative intensity at -21.77 ppm can be attributed to the formed O-Si-O bonds. Such siloxanes are expected to be between -20 and -25 ppm, which fits the found 29Si shift. Negative intensities are often observed for O-Si-O bonds in polymers and are caused by the negative nuclear Overhauser effect. The obtained intensities and integrals of the XPS, NMR, and FTIR spectra cannot be taken at face value to get quantitative information on the polymer's composition since all these three analytic methods are intrinsically different, as seen in Figure ig. While the X-rays of the XPS only penetrate the first 9 nm of the surface, the IR waves penetrate up to 1500 nm into the polymer, giving more information on the bulk composition than the FTIR. The 29Si NMR spectrum also does not allow a quantitative statement of the silicon species through the 29Si NMR experiment due to the NOE effect and the 1H NMR signals overlap, which makes integration difficult (see Figure le). Nevertheless, a higher oxidation state of the silicon on the surface of the polymer is probable since the surface is exposed to the oxygen in the air after deposition. Of note, the 1H NMR shown in Figure le also proves the composition of the polymer Parylene SiH, where the proton signals are assigned to the silane and the siloxane.

[0140]

[0108] When comparing the FTIR and XPS spectra, the signal ratios of the silane to the siloxane amounts do not match. While the X-rays of the XPS only give information of the first 9 nm (depth) of the surface, the FTIR allows for analysis of roughly the first isoonm. Knowing this, the conclusion can be drawn that the polymer is in higher oxidation states on the surface and in lower oxidation states deeper down. This is a reasonable assumption as the surface is exposed to oxygen after deposition, and the layers beneath are not. However, Si-O-Si vibrations in the FTIR are generally less intensive than Si-H or Si-Me vibrations; therefore, the intensity of the signal is not linearly correlated with the quantity of the groups in the polymer film. Therefore, the siloxane groups are underrepresented in the FTIR due to the intrinsically lower signal intensities of these groups. In the performed29Si (INTEPT) NMR, silicon atoms directly bound to hydrogen are higher in intensity, and the previously mentioned negative NOE does not allow a quantitative statement of the silicon species through the29Si NMR experiment. Nevertheless, a higher oxidation state of the silicon on the surface of the polymer is possible. Example 3: Influence of the Si-H bond

[0141]

[0109] To rationalize the role of the -SiMe2H substituent in this siloxane formation, we carried out quantum chemical calculation, on the model system dimethyl(phenyl)silane (Ml) as seen in Figure 2. For computational details, please refer to the Supporting Information. In general, calculations show the formation of -0-Si(Me)2-0-Si(Me2)-0- under elimination of water. The reaction of two Si-H moieties with a molecule of oxygen is energetically very favorable. The free energy for such a reaction, forming half equivalent of the corresponding diphenoxydisiloxane and half equivalent of water, is -131.7 kcal mol1. Based on the calculations, we propose that the Si-H moiety acts as a functional group that allows the initial reaction with 02under the LP-CVD conditions and essentially results in the condensation of the -SiMe2H substituent. According to the calculations, dioxygen in its ground triplet state can abstract a hydrogen atom from the - SiMe2H of dimethyl(phenyl)silane Ml, forming the corresponding silyl radical M2 and the hydroperoxyl radical (H00-) M3 at 40.3 kcal mol1. This step proceeds via a triplet transition state TSi at 41.5 kcal mol1, which is by 3.3 kcal mol1lower than the singlet diradical transition state that would result from the reaction with singlet oxygen. The radical coupling of M2 and M3 yields the hydroperoxydimethyl(phenyl)silane M4 at -36.2 kcal mol1. M4 can then rearrange via a barrier of 35.1 kcal mol (TS2, at -1.1 kcal mol1), in a highly exergonic fashion, to the corresponding dimethyl(phenoxy)silanol M5 (at -127.8 kcal mol1). This step corresponds to the insertion of the geminal oxygen atom into the Si-Ph bond. The oxygen atom insertion into the Si- Ph bond is thermodynamically and kinetically preferable over the analogous insertion into Si-Me bond by 10.4 and 5.3 kcal mol1, respectively. Calculations show that the dimethyl (phenoxy)silanol species M5 can condense to a half equivalent of compound M6, via TS3 (at -109.5 kcal mol1), which can then release a water molecule to form the final diphenoxydisiloxane product M6 at - 131.7 kcal mol1. Thus, calculations suggest that the Si-H moiety is essential for the initial reaction of the silyl-substituted aryl with oxygen, which can take place in the reaction chamber and initiate the formation of the diphenoxydisiloxane bridging unit via the proposed reaction mechanism. Such a process, which involves a hydrogen atom abstraction and the formation of the hydroperoxydimethyl(phenyl)silane at the first state, should not be possible in the case of the trimethylsilyl-substituted precursor.

[0142]

[0110] To confirm this hypothesis experimentally, we produced the trimethyl silyl functionalized parylene (parylene TMS) through the same process as parylene SiH. The XPS and NMR analysis showed that a significantly smaller amount of silicon is oxidized during the LP-CVD for parylene TMS compared to parylene SiH, which supported the discussed calculation further. Parylene TMS is also obtained as a very brittle polymer film that breaks easily under stress, suggesting less internal bonding.

[0143] Example 4: Properties of Parylene SiH and Post Modification

[0111] Parylene SiH has, besides minor extractables with roughly 560 g / mol a extremely high average molecular weight between Mn= 480.000 and 680.000 g / mol with a weight-averaged molecular weight of up to Mw= 1.870.000 g / mol, which was on the outer limits of the GPC method used. This is one reason why parylene SiH is insoluble in most organic solvents. Only non-polar solvents are able to swell or dissolve the polymer partially. Benzene was found to be the best solvent for parylene SiH, similar to parylene C, as it is able to dissolve around 3 mg in 0.5 mL.

[0144]

[0112] Parylene SiH is fully transparent as seen in the UV-Vis spectrum recorded (Figure 5), since no light from the region 300 - 1000 nm is absorbed.

[0145]

[0113] A main feature of parylene SiH is its flexibility and softness. Compared to parylene C, which has a Young's Modulus of 3.44 GPa in the setup used, parylenes SiH is considerably softer with its Young's Modulus of 2.86 GPa (see Table 1). Longer sidechains commonly lower the young modulus of a polymer since they usually lower crystallinity. Moreover, while being softer, parylene SiH is also more searchable than parylene C. The maximal elongation observed for parlyene C was between 20 and 30%, while parylene SiH could be elongated between 65 and 90 % before the polymer film breaks (see Figure 3g). The data sheet for parylene C gives a value for the elongation of up to 200%, many research groups struggled to reproduce this value and achieved elongations of 7.5 to 40 %, which are similar to the values found in this work . Parylene SiH is, with the in this work described method, is significantly more flexible and softer compared to parylene C. The dielectric constant of 3.11 of parylene SiH and 2.93 of parylene C at 1.0 MHz are comparable. Thus, a major impact on the electric properties of the hydrosilane group could be observed.

[0146]

[0114] Table 1: Comparison of properties of parylene C, parylene SiH, and parylene TMS found. With * marked values were taken from the literature.

[0147] Parylene C Parylene SiH Parylene TMS

[0148] Decomposition Temp [°C] 483 486 466

[0149] Glass Transition Temp [°C] 71.8 54.2 77.2

[0150] Youngs Modulus [GPa] 3.44 1.18 2.86

[0151] Elongation to break [%] 20 - 30 60 - 90 2 - 10

[0152] Contact Angle [°] 85.2 ± 0.9 95.1 ± 1.2 99.3 ± 3.6

[0153] Dielectric Constant (1 MHz) 2.93 3.11

[0154] Dielectric Constant (100 kHz) 2.95 3.05

[0155] Example 5: Post modification parylene SiH

[0115] An additional benefit of the Si-H functionalization is the possibility of post-modification of the polymer surface. Several different oxidation techniques, ranging from oxygen plasma, irradiation, and treatment with oxidizing agents, were carried out to investigate this. Here, the most control over the amount of post-modification gave oxygen plasma treatment for one, five, and ten minutes with the setup seen in Figure 3i. After one minute, all Si-H bonds were oxidized on the paiylene SiHs surface. Most Si-H bonds were transformed to fully oxidized Si- (0)4as seen in Figure 3a. This signal can be observed in the XPS at a bonding energy of 103.8 eV. Also, the twice oxidized Si-(0)2can be seen at 101.9 eV. After 10 minutes of oxygen plasma treatment, the surface of the parylene SiH is fully oxidized, and no silicon species other than Si-(O)4are left. Figure 3 a proves that we already have siloxane in the polymer after CVD and also shows the binding energy for the silane group. Figure 3a further proves that the inventors fully oxidized the silicon atoms with oxygen plasma. After 1 minute, the binding energy for the unoxidized Paiylene SiH cannot be found anymore.

[0156]

[0116] The increase in siloxane bonds can also be observed in the FTIRs recorded (Figure 3c). However, in addition to the intensified signal between 1000 and 1200 cm1, which corresponds to the stretching of Si-0 bonds, the Si-H vibration at 2115 cm1is almost unchanged in intensity. Since the oxygen plasma cannot go through the polymer layers, only the surface is oxidized, and the unoxidized Si-H bonds beneath them are still observable in the FITR.

[0157]

[0117] No NMR spectra could be obtained after oxygen plasma treatment because the polymer became practically insoluble in benzene after one minute of treatment, as seen in Figure 3j. This highlights a further property of parylene SiH. With only one minute of oxygen plasma treatment, the polymer surface could be changed to be even more resistant to organic solvents.

[0158]

[0118] To investigate the overall etching behavior of parylene SiH in oxygen plasma, the polymer was deposited on a silicon wafer and treated for one to 10 minutes under the same conditions and scanned by an atomic force microscope (AFM). Here, it can be observed that in general, the roughness of Paiylene SiH is increased when treating it with oxygen plasma. However, the roughness does not increase in the first minute of treatment as seen in Figure 3f. After 10 minutes of treatment, the initial surface mean roughness increased from 0.3 nm to 8.5 nm. Therefore, this AFM proves that 1 minute is a good time span for plasma treatment because we already get a lot of siloxane formation without damaging the polymer film.

[0159]

[0119] However, the increase in roughness does not go hand in hand with a decrease in polymer thickness, as it is common for commercially used parylenes. To investigate this behavior, parylene SiH and parylene C were treated for up to 65 minutes with oxygen plasma. After the full 65 minutes of exposure to oxygen plasma, only 50 to 60 nm of thickness was removed from parylene SiH. Paiylene C lost between 1200 nm and 1700 nm of its thickness during the same time, as seen in Figure yd.

[0160]

[0120] The reason behind the etch resistance of parylene SiH is most likely due to the passivation of the surface. When oxygen plasma first comes in contact with the surface of parylene SiH or parylene C, C-C bonds get cleaved through oxidation, and the oxidized fragments are removed by the vacuum in the plasma chamber. However, for parylene SiH, the silicon gets oxidized and forms a protective layer of fully oxidized silicon on the surface, which passivates the material and shields the parylene SiH beneath, as seen in Figure 7a and Figure 7c.

[0161]

[0121] This passivation is also observable in the full XPS spectra of the treated parylene SiH films (Figure 4b). While the untreated film has carbon as the main surface element, the treated films show mainly bonding energies for oxygen and silicon.

[0162]

[0122] An additional thermogravimetric analysis was carried out to investigate if the surface crosslinking increases the thermal stability of parylene SiH, which possesses in its untreated form a similar thermal stability as parylene C. Here, no significant change could be observed in thermal stability (see Figure 3k). The same analysis was performed with parylene C, but also here, no change could be observed. When performing a TGA, the polymers are heated under argon while the polymer is being weighed. When the polymer decomposes, a weight loss can be observed. Figure 3k demonstrates that Parylene SiH is comparable to Parylene C in terms of thermal stability. Moreover, the plasma treatment does not affect the decomposition temperature of Parylene C or Parylene SiH too much.

[0163]

[0123] Since oxygen plasma chambers are an expensive acquisition, additional chemical oxidation agents were tested. Here, aquatic potassium permanganate, hydrogen peroxide, and sodium hydrogen chloride were all suitable for the surface oxidation of parylene SiH. For this oxidation experiment, the parylene SiH film was immersed in the oxidation solution and left there for between one to three days. All three different solutions led to three different oxidized surfaces. While the KMnO (aq.) solution led to the formation of not only siloxane but also lead to silanol and K-0 and K+species, it also colored the polymer's surface pale brown due to the formation of Mn02, which is not ideal if a transparent polymer film is needed. After the treatment with H202(aq.), single oxidation of the silicone atoms occurs, as seen in the XPS spectrum in Figure 3b. However, this oxidation is not controllable, and sometimes, after multiple days in the solution, no oxidation at all occurs. Sometimes, after a few hours, the oxidation surface seen above was obtained. The reason for this unreliable oxidation could not be elucidated. The most promising and repeatable oxidation can be achieved using NaOCl (aq.). After 24 hours in the solution, only fully oxidized silicon can be observed in the XPS. Furthermore, next to the intense signals for siloxane bonds between 1000 and 1200 cm1in the FTIR, no signal for the SiH bond can be observed (see Figure 3d). This indicates that the perchlorate can also oxidize the SiH bonds, which are underneath the surface of the polymer, by penetrating deeper into the polymer. This oxidization led to a highly improved stretchability of the polymer film. Importantly, with possible elongation of over 120%, the NaOCl-treated Parylene SiH was the most stretchable. Figure 3d further demonstrates that different oxidized silicon species form when treated with different oxidizing agents. Therefore, surface modification is possible with oxygen plasma and chemical oxidizing agents.

[0124] When placing Parylene C or other Parylenes in an oxygen plasma chamber, the oxygen plasma breaks the bonds of the surface and removes the polymer molecule by molecule. Therefore, you can theoretically remove 1 micrometer of Parylene C when leaving it for an hour in the plasma chamber. As seen in Figure 3e, with Parylene SiH, this is not possible, as the formation of siloxane bonds prevents the etching.

[0164]

[0125] Since oxygen plasma and aquatic NaOCl (aq.) were the most controllable oxidation techniques, tensile tests were conducted with the treated films. The already stretchable and soft parylene SiH becomes more stretchable and softer after one minute of oxygen plasma treatment, as seen in Figure 3g and Figure 3I1. Figure 3g showcases the flexible nature of Parylene SiH and the impact of the post-modification on flexibility. Figure 3I1 showcases the unflexible nature when replacing the hydrogen of Parylene SiH by a methyl group.

[0165]

[0126] Longer exposure to oxygen plasma does not enhance this effect, and at a treatment time of 10 minutes, the parylene SiH films become less stretchable. The NaOCl (aq.) treated film has also increased stretchability with an elongation at break at around 120 %. Parylene TMS breaks already after an elongation of 10 %. This highlights the importance of the Si-H bond in parylene SiH. Either through crosslinking processes or through the different sizes of the side chain, parylene SiH becomes highly flexible. Also, internal hydrogen bonding is a possible factor in the polymer’s mechanical properties.

[0166] Example 6: Effect of the Si-H groups

[0167]

[0127] To investigate the role of the Si-H bond of paiylene SiH on its polymerization mechanism and its properties, the derivate trimethyl silane functionalized parylene (parylene TMS) was synthesized. Here, three methyl groups are attached to the silicon atom instead of the two methyl groups and one hydrogen. Parylene TMS is a transparent and delicate film that quickly breaks under stress. With the same analytic methods used to characterize parylene SiH, it was found that parylene TMS also develops siloxane bonds during polymerization. However, in parylene TMS they are significantly less present. While the signals for the siloxanes in parylene TMS are found in the same region as in Parylene SiH, the intensities and integrals are only a fraction of parylene SiHs. So, the oxidation of the silicon atom is possible without the Si-H bond but is less favored.

[0168]

[0128] Fig. 4 c shows the successful synthesis of the SiH dimer. Only see the expected signal can be observed, but no side products. Therefore, the synthesis with t-BuLi and HSiMe2Cl is suitable to produce the SiH dimer. Fig. 4 d proves the successful synthesis of SiH dimer. Only expected signals with the expected integrals can be observed, but no side products. Therefore, the synthesis with t-BuLi and HSiMe2Cl is suitable to produce the SiH dimer. Fig. 4e proves the purity of the product obtained of the synthesis route according to the present invention. The left values 74,00 (crabon), 8,59 (hydrogen), 17,30 (silicon) are the expected mass percentage of the elements and the most right values 73,97 (carbon) and 8,58 (hydrogen) are the found mass percentage. Fig. 4f further proves that the inventors have, in fact, synthesized the right dimer, since the SiMe2H groups are attached to the expected carbons.

[0129] The crystallographic details of 4,i6-bis(dimethylsilyl)[2.2]paracyclophane and 4,16- bis(trimethylsilyl)[2.2]paracyclophane are shown in Table 2 below.

[0169] Table 2: Crystallographic details of 4,i6-bis(dimethylsilyl)[2.2]paracyclophane and 4,16- bis(trimethylsilyl)[2.2]paracyclophane.

[0170] REFERENCES

[0171] The references are:

[0172] [1] P. Sivakumar, S. M. Du, M. Selter, I. Ballard, J. Daye, J. Cho, Polymer Degradation and Stability 2021, 191, 109667.

[0173] [2] M. Golda-Cepa, K. Engvall, M. Hakkarainen, A. Kotarba, Progress in Organic Coatings 2020, 140, 105493.

[0174] [3] Jeffrey B. Fortin, Chemical Vapor Deposition Polymerization, 2004.

[0175] [4] Maciej GAZICKI-LIPMAN, Journal of the Vacuum Society of Japan 2006, 601-608.

[0176] [5] Fang-Yu Chou, Theresia Cecylia Ramli, Chin-Yun Lee, Shu-Man Hu, Jane Christy, Hsien-Yeh Chen, Organic Materials 2023, 118-138.

[0177] [6] Jui-Mei Hsu, Loren Rieth, Sascha Kammer, Sensors and Materials 2008, 87-102.

[0178] [7] L. Sun, G. Yuan, L. Gao, J. Yang, M. Chhowalla, M. H. Gharahcheshmeh, K. K. Gleason, Y. S. Choi, B. H. Hong, Z. Liu, Nat Rev Methods Primers 2021, 1.

[0179] [8] IntechOpen, Ed, Chemical Vapor Depostition: Recent Advances and Applications in Optical, Solar cells and Solid state Devices, 2016.

[0180] [9] G. Lee, S. C. Jang, J. H. Lee, J.-M. Park, B. Noh, H. Choi, H. Kweon, D. H. Kim, H. Y. Kim, H.-S. Kim, K. J. Lee, Adv Funct Materials 2024.

[0181]

[0010] J. J. Senkevich, B. W. Woods, J. J. McMahon, P.-I. Wang, Chemical Vapor Deposition 2007, 13, 55-59-

[0182]

[0011] I. Sanzari, M. Callisti, A. de Grazia, D. J. Evans, T. Polcar, T. Prodromakis, Scientific reports 2017, 7, 5764.

[0183]

[0012] M. Golda, M. Brzychczy-Wloch, M. Faryna, K. Engvall, A. Kotarba, Materials science & engineering. C, Materials for biological applications 2013, 33, 4221-4227.

Claims

1. Claims1. A polymer comprising the structure according to the formula (I):wherein Ri is selected from the group consisting of hydrogen, C1-C6 alkyl (preferably methyl), C1-C6 alkenyl, C1-C6 alkynyl, C3-C6 cycloalkyl (preferably phenyl), C3-C6 heterocyclyl, hydroxyl, hydroxymethyl, halogen, e. g. Cl or F, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e. g. OMe, or OCF3, and C1-C6 haloalkyl, e.g. CH2F, CHF2, CF3, CH2CF3, any of which is unsubstituted or substituted with one or several groups selected from halogen, e.g. Cl or F, C1-C6 alkyl, C1-C6 haloalkyl, e. g. CH2F, CHF2, CF3, CH2CF3, hydroxymethyl, hydroxyl, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e.g. OMe, or OCF3, and combinations thereof; wherein R2is selected from the group consisting of hydrogen, C1-C6 alkyl (preferably methyl), C1-C6 alkenyl, C1-C6 alkynyl, C3-C6 cycloalkyl (preferably phenyl), C3-C6 heterocyclyl, hydroxyl, hydroxymethyl, halogen, e. g. Cl or F, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e. g. OMe, or OCF3, and C1-C6 haloalkyl, e.g. CH2F, CHF2, CF3, CH2CF3, any of which is unsubstituted or substituted with one or several groups selected from halogen, e.g. Cl or F, C1-C6 alkyl, C1-C6 haloalkyl, e. g. CH2F, CHF2, CF3, CH2CF3, hydroxymethyl, hydroxyl, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e.g. OMe, or OCF3, and combinations thereof, and wherein R3is selected from the group consisting of hydrogen, C1-C6 alkyl (preferably methyl), C1-C6 alkenyl, C1-C6 alkynyl, C3-C6 cycloalkyl (preferably phenyl), C3-C6 heterocyclyl, hydroxyl, hydroxymethyl, halogen, e. g. Cl or F, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e. g. OMe, or OCF3, and C1-C6 haloalkyl, e.g. CH2F, CHF2, CF3, CH2CF3, any of which is unsubstituted or substituted with one or several groups selected from halogen, e.g. Cl or F, C1-C6 alkyl, C1-C6 haloalkyl, e. g. CH2F, CHF2, CF3, CH2CF3, hydroxymethyl, hydroxyl, COOMe, C(O)H, COOH, alkoxy, in particular C1-C3 alkoxy, e.g. OMe, or OCF3, and combinations thereof.

2. The polymer according to claim 1, wherein one of Ri, R2, and R3is hydrogen.

3. The polymer according to claim 1 or 2, wherein Ri is hydrogen, R2is methyl and R3is methyl, and wherein the polymer comprises the structure according to the formula (II):4- The polymer according to any one of claims 1 to 3, wherein the polymer is a crosslinked, a transparent, a flexible, a stretchable, and / or an etch-resistant polymer, and / or wherein the polymer is modifiable post polymerization, such as modifiable through oxygen plasma and / or chemical oxidizing agents.

5. A process of manufacturing a polymer, preferably a polymer according to any one of claims 1 to 4, comprising the steps of:(a) Providing paracyclophane, 4,i2-dibromo[2.2]paracyclophane and / or 4,12- diiodo[2.2]paracyclophane;(b) Optionally, treating paracyclophane with Br2and / or I2, thereby obtaining 4,12- dibromo[2.2]paracyclophane and / or 4,i2-diiodo[2.2]paracyclophane;(c) Functionalizing 4,i2-dibromo[2.2]paracyclophane and / or 4,12- diiodo[2.2]paracyclophane, wherein the functionalizing comprises the step of treating 4,i2-dibromo[2.2]paracyclophane and / or 4,12- diiodo[2.2]paracyclophane with t-BuLi, n-BuLi, SiClRiR2R3, HSiClR2R3, and / or HSiClMe2, in a solvent, such as Tetrahydrofuran (THF), Diethyl ether, Hexane, Pentane, Toluol, or a solvent mixture thereof, thereby obtaining a dimer according to formula (III);(d) Purifying the dimer obtained in step (c), such as purifying the dimer obtained in step (c) by sublimating the dimer, wherein the sublimating preferably occurs at a temperature range and / or a pressure range, preferably wherein the temperature range is between i6o°C and 200°C, more preferably between 165°C and i8o°C, and / or preferably wherein the pressure range is preferably between 0.02 and 0.10 mbar, more preferably around 0.04 mbar, thereby obtaining a purified dimer according to formula (III);(e) Polymerizing the purified dimer obtained in step (d), such as by chemical vapor deposition, thereby obtaining a polymer, and(f) Optionally, additional surface-crosslinking of the polymer as obtained in step (e), preferably wherein said surface-crosslinking is achieved by oxygen plasma treatment, H202(aq.), NaOCl (aq.), and / or KMnO4(aq.), thereby obtaining a surface-crosslinked polymer.

6. The process of manufacturing according to claim 5, wherein the treating in step b) comprises a treatment duration of between 3 and 5 hours, optionally wherein the treating in step b) occurs at a temperature range of between 55°C and 75°C, and / or wherein the stoichiometric ratio of paracyclophane to Br2is between 1.0 to 6.0 and 1.0 to 6.5, further optionally wherein the treating in step b) occurs in presence of CHCI3.

7. The process of manufacturing according to claim 5 or 6, wherein the functionalizing in step (c) comprises:(i) Suspending 4,i2-dibromo[2.2]paracyclophane and / or 4,12- diiodo[2.2]paracyclophane in a solvent, such as Tetrahydrofuran (THF), Diethyl ether, Hexane, Pentane, Toluol, or a solvent mixture thereof, thereby obtaining a suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,12- diiodo[2.2]paracyclophane;(ii) Adding t-BuLi to the suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane obtained in step (i) at a first temperature range and stirring for a first time period to obtain a first mixture, wherein the first temperature range is between -78°C and -65°C, preferably wherein the stoichiometric ratio of 4,i2-dibromo[2.2]paracyclophane or 4,12- diiodo[2.2]paracyclophane to t-BuLi is between 1.0 to 4.0 and 1.0 to 4.5, more preferably wherein the stoichiometric ratio of 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane to t-BuLi is around 1.0 to 4.1, optionally wherein the molarity of t-BuLi is around 1.6 M;(iii) Stirring the first mixture for 10 to 60 minutes, preferably for 15 minutes, at a second temperature range, wherein the second temperature range is between -io°C to 5°C, preferably around o°C;(iv) Adding SiClRiR2R3, HSiClR2R3, and / or HSiClMe2, to the first mixture obtained in step (iii) at a third temperature range to obtain a second mixture, wherein the third temperature range is between -78°C and -65°C, wherein the stoichiometric ratio of SiClRiR2R3, HSiClR2R3, and / or HSiClMe2to 4,12- dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane is between 1.0to 4.0 and 1.0 to 4.5, more preferably wherein the stoichiometric ratio is around 1.0 to 4.1, thereby obtaining a third mixture;(v) Stirring the third mixture at a fourth temperature range, wherein the fourth temperature range is between 20°C and 3O°C, optionally wherein the time period of the stirring is between 16 and 24 hours;(vi) Optionally, removing the solvent from the third mixture to obtain a product, and(vii) Further optionally, purifying the product, such as purifying the product by sublimating the product.

8. The process of manufacturing according to claim 5 or 6, wherein the functionalizing in step (c) comprises:(i) Suspending 4,i2-dibromo[2.2]paracyclophane and / or 4,12- diiodo[2.2]paracyclophane in a solvent, such as Tetrahydrofuran (THF), Diethyl ether, Hexane, Pentane, Toluol, or a solvent mixture thereof, thereby obtaining a suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,12- diiodo[2.2]paracyclophane;(ii) Adding n-BuLi to the suspension comprising 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane obtained in step (i) at a first temperature range, wherein the first temperature range is between -78°C and -65°C, optionally wherein the stoichiometric ratio of 4,i2-dibromo[2.2]paracyclophane or 4,12- diiodo[2.2]paracyclophane to n-BuLi is between 1.0 to 6.0 and 1.0 to 8.0, preferably wherein the stoichiometric ratio of 4,i2-dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane to n-BuLi is around 1.0 to 8.0, further optionally wherein the molarity of n-BuLi is around 1.6 M;(iii) Stirring the first mixture for 1 to 3 hours at a second temperature range, wherein the second temperature range is between 3O°C to -4O°C;(iv) Adding SiClRiR2R3, HSiClR2R3, and / or HSiClMe2, to the first mixture obtained in step (iii) at a third temperature range to obtain a second mixture, wherein the third temperature range is between -78°C and -65°C, wherein the stoichiometric ratio of SiClRiR2R3, HSiClR2R3, and / or HSiClMe2to 4,12- dibromo[2.2]paracyclophane or 4,i2-diiodo[2.2]paracyclophane is between 1.0 to 6.0 and 1.0 to 8.0, more preferably wherein the stoichiometric ratio is around 1.0 to 4.1, thereby obtaining a third mixture;(v) Stirring the third mixture at a fourth temperature range, wherein the fourth temperature range is between 20°C and 3O°C, for 16 to 24 hours;(vi) Optionally, removing the solvent from the third mixture to obtain a product, and(vii) Further optionally, purifying the product, such as purifying the product by sublimating the product.

9. The process of manufacturing according to any one of claims 5 to 8, wherein the dimer obtained in step c) is 4,i6-bis(dimethylsilyl)[2.2]paracyclophane, having a structure according to formula (IV):

10. The process of manufacturing according to any one of claims 5 to 9, wherein the polymer as obtained in step (e) comprises a mixture of a polymer comprising the structure according to the formula (II) and a polymer comprising the structure according to the formula (VI):

11. The process of manufacturing according to any one of claims 5 to 10, wherein the surface-crosslinked polymer obtained in step f) has a structure according to the formula (VII), optionally wherein a further product obtained in step f) is a polymer comprising a structure according to the formula (V):optionally12. The process of manufacturing according to any one of claims 5 to 11, wherein the yield of the surface-crosslinked polymer as obtained in step (f) of the method depends on the treatment time, the treatment agent, and / or the amount of functionalizing as performed in step (c), and wherein the crosslinking depends on the amount of oxygen present in the chemical vapor deposition.

13. The process of manufacturing according to any one of claims 5 to 12, wherein the additional surface-crosslinking in step (f) enhances the molecular mass of the polymer, optionally wherein the higher molecular mass of the surface-crosslinked polymer enhances the stability of the surface-crosslinked polymer towards a solvent, increases the hydrophobicity of the polymer, and / or alters the mechanical properties of the of the polymer.

14. A polymer obtained by a process according to any one of claims 5 to 13.

15. A polymer, preferably a polymer according to claim 14, having a structure according to any one of formula (II), formula (V), formula (VI), and / or formula (VII):

16. A surface crosslinked polymer, preferably a surface-crosslinked polymer obtained by a process according to any one of claims 5 to 13, comprising the structure according to the formula (VI) or the formula (VII):crosslinked polymer according to claim 16, for coatings of electronics, medical instruments, implants, protection coatings for materials, coatings for glass, in the pharmaceutical industry, battery technology, construction chemistry, and aerospace applications.

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