Modified guayule resin products and related processes

Abstract

Disclosed herein is a modified guayule resin product and related processes for preparing the modified guayule resin product. The modified guayule resin product comprises a mixture of argentatins having at least one functional group, the at least one functional group being provided by a functionalizing compound selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes. In a second embodiment, a process for preparing a modified guayule resin product is provided, in which a guayule resin component (including a mixture of argentatins) is mixed with a functionalizing compound selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes to produce a modified guayule resin comprising a functionalized argentatin having at least one functional group provided by the functionalizing compound.

Description

[Technical field]

[0001] This application is directed to modified guayule resin products and related processes for preparing modified guayule resin products. Summary of the Invention

[0002] The guayule plant (Parthenium argentatum) is a woody, shrub-like plant that produces rubber and resin. Processes aimed at isolating rubber from the guayule plant produce significant amounts of guayule resin as a by-product.

[0003] Disclosed herein are modified guayule resin products and related processes for preparing the modified guayule resin products.

[0004] In a first embodiment, a modified guayule resin product is provided that comprises a mixture of argentatin having at least one functional group, the at least one functional group being provided by a functionalizing compound selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes.

[0005] In a second embodiment, a process for preparing a modified guayule resin product is provided. According to the process of the second embodiment, a guayule resin component is provided that comprises a mixture of argentatins having -OH groups. The guayule resin component is mixed with a functionalizing compound selected from an alkoxysilane, a mercaptosilane, and a blocked mercaptosilane to produce a modified guayule resin that comprises a functionalized argentatin having at least one functional group provided by the functionalizing compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] Disclosed herein are modified guayule resin products and related processes for preparing the modified guayule resin products.

[0007] In a first embodiment, a modified guayule resin product is provided that comprises a mixture of argentatin having at least one functional group, the at least one functional group being provided by a functionalizing compound selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes.

[0008] In a second embodiment, a process for preparing a modified guayule resin product is provided. According to the process of the second embodiment, a guayule resin component is provided that comprises a mixture of argentatins having -OH groups. The guayule resin component is mixed with a functionalizing compound selected from an alkoxysilane, a mercaptosilane, and a blocked mercaptosilane to produce a modified guayule resin that comprises a functionalized argentatin having at least one functional group provided by the functionalizing compound.

[0009] definition The terminology used herein is for the purpose of describing the embodiments only and is not to be construed as limiting the invention as a whole.

[0010] As used herein, the term "BR" or "polybutadiene" refers to a homopolymer of 1,3-butadiene.

[0011] As used herein, the term "major amount" refers to more than 50% (e.g., at least 50.1%, at least 50.5%, at least 51%, etc.).

[0012] As used herein, the term "less than half" refers to less than 50% (eg, 49.5% or less, 49% or less, etc.).

[0013] As used herein, the abbreviation Mn is used for number average molecular weight.

[0014] As used herein, the abbreviation Mp is used for peak molecular weight.

[0015] As used herein, the abbreviation Mw is used for weight average molecular weight.

[0016] Unless otherwise specified herein, the term "Mooney viscosity" refers to Mooney viscosity, ML 1+4 Those skilled in the art will appreciate that the Mooney viscosity of a rubber composition is measured prior to vulcanization or curing.

[0017] As used herein, the term "natural rubber" refers to naturally occurring rubber such as that which can be harvested from sources such as the Hevea rubber tree and from non-Hevea sources (e.g., the guayule plant and dandelion such as TKS). In other words, the term "natural rubber" should be interpreted to exclude synthetic polyisoprene.

[0018] As used herein, the term "guayule rubber" is a subclass of natural rubber harvested from the guayule plant. In contrast, natural rubber not harvested from the guayule plant is referred to herein as "non-guayule natural rubber" and can include hevea rubber as well as other sources such as dandelion.

[0019] As used herein, the term "phr" means parts per hundred of rubber. 100 parts of rubber is also referred to herein as 100 parts of the rubber component.

[0020] As used herein, the term "polyisoprene" refers to synthetic polyisoprene. In other words, the term is used to indicate a polymer made from isoprene monomers, and should not be construed to include naturally occurring rubbers (e.g., Hevea rubber, guayule rubber, or dandelion rubber). However, the term "polyisoprene" should be construed to include polyisoprene made from natural sources of isoprene monomers.

[0021] As used herein, the term "SBR" means styrene-butadiene copolymer rubber.

[0022] As used herein, the term "tread" refers to that portion of the tire that contacts the road under normal inflation and load, and the term "subtread" refers to the underlying portion of the tread that generally does not contact the road.

[0023] Modified guayule resin products As mentioned above, the first embodiment disclosed herein is directed to a modified guayule resin product, and the second embodiment disclosed herein provides a process for preparing the modified guayule resin product. According to the first and second embodiments, the modified guayule resin product comprises a mixture of argentatins having at least one functional group, the at least one functional group being provided by a functionalizing compound selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes. As will be appreciated by those skilled in the art, argentatins are naturally present in guayule resin and constitute a class of compounds that contain one or more -OH groups (in unmodified or non-functionalized form). These argentatins are classified into various categories, including argentatin A, argentatin B, argentatin C, argentatin D, argentatin E, and argentatin F. The modification or functionalization of argentatins is carried out by binding an oxygen atom from the -OH group of the argentatin compound to the silicon atom of the functionalizing compound. In other words, the point of attachment between the argentatin compound and the functionalizing compound is through an oxygen atom from the -OH group of the argentatin compound to the silicon atom of the functionalizing compound. As a non-limiting example, the use of a trialkoxysilane in the functionalizing compound results in the following modified or functionalized argentatin structure:

[0024] [ka] (where Arg-O refers to the argentatin compound without the hydrogen atom from its -OH group). The trialkoxysilane compound contains three alkoxy groups, thus providing three points of attachment to the argentatin compound. For argentatin compounds containing more than one -OH group, more than one point of attachment to the silicon atom of the alkoxysilane compound is possible. Overall, the bond between argentatin and the alkoxysilane compound (or more broadly, the functionalizing compound) results in a modified guayule resin product.

[0025] According to the first and second embodiments, the specific functionalizing compound used to functionalize Argentatin can vary. As mentioned above, according to the first and second embodiments, the functionalizing compound is selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes, each as discussed in more detail below.

[0026] According to the first and second embodiments, the mass percentage or weight percentage of hydrogen atoms from -OH groups of argentatin replaced by functional groups from the functionalizing compound can vary. In a preferred embodiment of the first and second embodiments, the mixture of functionalized argentatin in the modified guayule resin product has at least 50% by mass (e.g., 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or more) of hydrogen atoms from its -OH groups replaced by at least one functional group, preferably 60-90% by mass (e.g., 60, 65, 70, 75, 80, 85, or 90%) of hydrogen atoms from its -OH groups replaced by at least one functional group. The mass percentage of hydrogen atoms from -OH groups of the mixture of argentatin replaced by at least one functional group from the alkoxysilane can be considered as the functionalization percentage of the mixture of argentatin. In other words, a mixture of argentatin in which 75% by weight of the hydrogen atoms from the -OH groups have been replaced with functional groups from the functionalization can be considered to be 75% functionalized.

[0027] According to the first and second embodiments disclosed herein, the properties (e.g., Tg, Mn, and Mw) of the modified guayule resin product may vary. In certain embodiments of the first and second embodiments, the modified guayule resin product has a Tg of about -70 to 100°C (e.g., -70, -60, -50, -40, -30, -20, -10, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100°C). In certain embodiments of the first and second embodiments, the modified guayule resin product has a Tg within the lower portion of the aforementioned ranges, e.g., -60 to 0°C (e.g., -60, -55, -50, -45, -40, -35, -30, or 100°C). In other embodiments of the first and second embodiments, the modified guayule resin product has a Tg within the upper portion of the aforementioned range of -70 to 100°C, for example, 1 to 100°C (e.g., 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100°C), preferably 30 to 90°C (e.g., 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100°C). , 75, 80, 85, 90°C), more preferably from 40 to 90°C (e.g., 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90°C). Modified guayule resin products having a Tg within one of the aforementioned ranges may be particularly useful in tire rubber compositions, for example, for tread compounds. In certain embodiments of the first and second embodiments, the modified guayule resin products have a Tg of 2000 to 4500 grams / mole and 2500 to 4000 grams / mole. and having a Mn of 1600 to 5000 grams / mol (e.g., 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, or 5000 grams / mol).In certain embodiments of the first and second embodiments, the modified guayule resin product has a Mw of 2000 to 10,000 grams / mole (e.g., 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, or 10,000 grams / mole), including 4000 to 9000 grams / mole and 5000 to 8000 grams / mole. In certain embodiments of the first and second embodiments, the modified guayule resin has a Mw and Mn within the aforementioned ranges. In certain such embodiments, the modified guayule resin also has a Tg within one of the aforementioned ranges. The Mw and Mn values ​​can be determined by GPC, for example, using the methods described in the Examples. Tg values ​​can be determined by DSC using equipment such as that manufactured by TA Instruments (New Castle, Delaware), where measurements are performed using a 10°C / min temperature ramp after cooling at -120°C. A tangent is then drawn to the baseline before and after the jump in the DSC curve. The temperature on the DSC curve (read at the point corresponding to the middle of the two tangent points) can be used as the Tg.

[0028] According to the first and second embodiments, the amount of guayule rubber present in the modified guayule resin product may vary. As will be appreciated by those skilled in the art, the amount of guayule rubber present in the modified guayule resin product often depends on the amount of guayule rubber that was present in the (unmodified) guayule resin component from which the modified guayule resin product is prepared. However, the amount of guayule rubber present in the modified guayule resin product may also refer to guayule rubber added after functionalization of the guayule resin component. In certain embodiments of the first and second embodiments, the modified guayule resin product contains less than 10% by weight (e.g., 9.5%, 9%, 8.5%, 8%, 7.5%, 7%, 6.5%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, 0.5%, or less), preferably less than 5% by weight (e.g., 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, 0.5%, or less), or even less than 1% by weight guayule rubber.

[0029] According to the first and second embodiments disclosed herein, the weight percentage of functionalized argentatin in the modified guayule resin product can vary. Preferably, according to the first and second embodiments, the mixture of functionalized argentatins constitutes the major component by weight of the modified guayule resin product. Major component means that among the different components present in the modified guayule resin product (e.g. unmodified argentatin, triglycerides, fatty acids), the component present in the greatest amount is the functionalized argentatin component (which is generally a mixture of functionalized argentatins). In more preferred embodiments of the first and second embodiments, the mixture of functionalized argentatin constitutes at least 40% by weight of the modified guayule resin product (e.g., 40%, 50%, 60%, 70%, 80%, 90%, 95% or more), more preferably at least a majority by weight of the modified guayule resin product (e.g., 51%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or more), even more preferably at least 60% by weight of the modified guayule resin product (e.g., 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or more), or between 60 and 90% by weight of the modified guayule resin product (e.g., 60%, 65%, 70%, 75%, 80%, 85%, 90%). The amount of functionalized argentatin in the modified guayule resin product can be determined by GPC (e.g., using the procedures described in the Examples), where the functionalized argentatin is generally represented by at least the first eluting peak, and often at least a portion of the second eluting peak (functionalized argentatin generally has an Mn in the range of 1600-5000 grams / mole, as discussed below, and therefore one skilled in the art will understand how to interpret the GPC results to correspond to the amount of product within this Mn range). The modified guayule resin product may also contain some portion of triglycerides, fatty acids, and unmodified argentatin and guayule (the relative amounts will generally vary depending on the amount present in the unmodified guayule resin component and / or any purification processes performed on the modified guayule resin product to remove such materials).

[0030] Guayule Resin Products As mentioned above, the process of the second embodiment includes the use of a guayule resin product mixed with a functionalizing compound to produce a modified guayule resin product. Similarly, the modified guayule resin product of the first embodiment can be understood to be a functionalized version of the guayule resin product in which the functionalizing compound discussed herein is used. As mentioned above, the guayule resin product includes a mixture of argentatins having -OH groups. Preferably, according to the first and second embodiments, the mixture of argentatins constitutes the major component by weight of the guayule resin component. Major component means that of the different components present in the guayule resin component (e.g. argentatin, triglycerides, fatty acids, and low molecular weight rubbers), the component present in the greatest amount is the argentatin component (which is generally a mixture of argentatins). In more preferred embodiments of the first and second embodiments, the mixture of argentatin constitutes at least 40% by weight of the guayule resin component (e.g., 40%, 50%, 60%, 70%, 80%, 90%, 95% or more), more preferably at least a majority by weight of the guayule resin component (e.g., 51%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or more), even more preferably at least 60% by weight of the guayule resin component (e.g., 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or more), or between 60 and 90% by weight of the guayule resin component. Generally, due to the difficulty in separating the argentatin component of guayule resin from other naturally occurring components, the weight percentage of the guayule resin component that constitutes argentatin will be less than 100%.

[0031] According to the first and second embodiments, the amount of guayule rubber present in the guayule resin component can vary. In certain embodiments of the first and second embodiments, the guayule resin component contains less than 10% by weight (e.g., 9.5%, 9%, 8.5%, 8%, 7.5%, 7%, 6.5%, 6%, 5.5%, 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, 0.5%, or less), preferably less than 5% by weight (e.g., 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, 1%, 0.5%, or less), or even less than 1% by weight, of guayule rubber.

[0032] Compounds for functionalization As mentioned above, according to the first and second embodiments, the functionalizing compound is selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes. As will be discussed in more detail below, alkoxysilanes should be understood to include both sulfur-containing and non-sulfur-containing alkoxysilanes.

[0033] In certain embodiments of the first and second embodiments disclosed herein, the functionalizing compound is a non-sulfur-containing alkoxysilane. Preferably, according to such embodiments, the non-sulfur-containing alkoxysilane has the formula (I): R 1 (4-n) -Si(OR 2 ) n (I) (wherein n=2, 3, or 4; each R 1 are independently selected from hydrocarbyl groups having 1 to 20 carbons, preferably 2 to 18 carbons; R 2is an alkyl group having 1 to 10 carbons, preferably 1 to 6, more preferably 1 to 3 carbons, or an aromatic group having 6 to 18 carbons, preferably 6 to 12 carbons). When n=2, the non-sulfur-containing alkoxysilane can be understood to be a dialkoxysilane. When n=3, the non-sulfur-containing alkoxysilane can be understood to be a trialkoxysilane. When n=4, the non-sulfur-containing alkoxysilane can be understood to be a tetraalkoxysilane.

[0034] In certain embodiments of the first and second embodiments, the functionalizing compound is a non-sulfur-containing alkoxysilane, ie, a dialkoxysilane, having formula (I) where n=2. Non-limiting examples of non-sulfur-containing alkoxysilanes that are dialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dipentyldimethoxysilane, dipentyldiethoxysilane, dihexyldimethoxysilane, dihexyldiethoxysilane, diheptyldimethoxysilane, diheptyldiethoxysilane, dioctyldimethoxysilane, dioctyldiethoxysilane, dinonyldimethoxysilane, dinonyldiethoxysilane, didecyldimethoxysilane, didecyldiethoxysilane, diundecyldimethoxysilane, diethyl silane, diundecyl diethoxysilane, didodecyl dimethoxysilane, didodecyl diethoxysilane, ditridecyl dimethoxysilane, ditridecyl diethoxysilane, ditetradecyl dimethoxysilane, dipentadecyl dimethoxysilane, ditetradecyl diethoxysilane, dipentadecyl diethoxysilane, dihexadecyl dimethoxysilane, dihexadecyl diethoxysilane, diheptadecyl dimethoxy Silanes include, but are not limited to, diheptadecyldiethoxysilane, dioctadecyldimethoxysilane, dioctadecyldiethoxysilane, dinonadecyldimethoxysilane, dinonadecyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, dibenzyldimethoxysilane, and dibenzyldiethoxysilane.

[0035] In certain embodiments of the first and second embodiments, the functionalizing compound is a non-sulfur-containing alkoxysilane, ie, a trialkoxysilane, having formula (I) where n=3. Non-limiting examples of non-sulfur-containing alkoxysilanes that are trialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltripoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undec ... Examples of suitable silanes include, but are not limited to, butylsilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripoxysilane, phenyltriisopropoxysilane, benzyltrimethoxysilane, and benzyltriethoxysilane.

[0036] In certain embodiments of the first and second embodiments, the functionalizing compound is a non-sulfur-containing alkoxysilane having formula (I) where n=4, i.e., a tetraalkoxysilane. Non-limiting examples of non-sulfur-containing alkoxysilanes that are tetraalkoxysilanes include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetraisobutoxysilane.

[0037] In certain embodiments of the first and second embodiments disclosed herein, the functionalizing compound is a non-sulfur-containing bisalkoxysilane. A non-sulfur-containing bisalkoxysilane can be understood as containing two silicon atoms, preferably separated by a divalent hydrocarbyl group, with each silicon atom having two or three alkoxy groups. In certain embodiments of the first and second embodiments, the non-sulfur-containing bisalkoxysilane has the formula (Y)G(Z), where G is C 1 ~C 50 Linear and branched alkylene, C 2 ~C 50 Linear and branched alkenylene, C 6 ~C 50 aromatic, each optionally containing a heteroatom selected from the group consisting of one or more O or one or more N, and combinations thereof; Y and Z may be the same or different and each independently represent a group of formula Si(R 7 ) p (OR 8 ) 3-p (In the formula, each R 7 is independently 1 ~C 20 aliphatic, alicyclic, or aromatic, R 8 is C 1 ~C 6 aliphatic or cycloaliphatic, and p is an integer of 0 or 1. In a preferred embodiment of the first and second embodiments, when the non-sulfur-containing bisalkoxysilane has the above formula, G of the non-elastomeric reactive filler reinforcing agent comprises a group of C 2 ~C 20Alkylene, alkenylene, and C 6 ~C 20 aromatic, each optionally containing a heteroatom selected from the group consisting of one or more O or one or more N, and combinations thereof. In certain embodiments of the first and second embodiments, the non-sulfur-containing bisalkoxysilane has the formula (Y)G(Z), where G is C 6 ~C 20 each R is selected from the group consisting of alkylene and alkenylene; 8 is C 1 ~C 6 In certain embodiments of the first and second embodiments, the non-sulfur-containing bisalkoxysilane has the formula (Y)G(Z), where G is selected from the group consisting of C 4 ~C 20 Linear and branched alkylene, and C 4 ~C 20 In certain embodiments, the non-sulfur-containing bisalkoxysilane is selected from the group consisting of linear and branched alkenylenes, both of which optionally contain additional carbon atoms in the form of one or more aromatic rings. 1 ~C 6 (i.e., methyl to hexyl), preferably C 1 ~C 3 , and even more preferably C 1 ~C 2Specific examples of such bis(trialkoxy)silanes include bis(trimethoxysilyl)ethane, bis(triethoxysilyl)ethane, bis(tributoxysilylethane, bis(triethoxysilyl)propane, bis(trimethoxysilyl)propane, bis(tributoxysilylpropane, bis(triethoxysilyl)butane, bis(trimethoxysilyl)butane, bis(tributoxysilylbutane, bis(triethoxysilyl)isobutane, bis(trimethoxysilyl)isobutane, bis(tributoxysilylisobutane, bis(triethoxysilyl)hexane, bis(trimethoxysilyl)hexane, bis(tributoxysilylhexane, bis(triethoxysilyl)cyclohexane, bis(trimethoxysilyl)cyclohexane, bis(tributoxysilylcyclohexane, bis(trimethoxysilyl)heptane, bis(triethoxysilyl)cyclohexane, bis(triethoxysilyl)cyclohexane, bis(tributoxysilylcyclohexane, bis(trimethoxysilyl)heptane, bis(triethoxysilyl)cyclohexane, bis(triethoxysilyl)cyclohexane, bis(trimethoxysilyl)cyclohexane, bis(tributoxysilylcyclohexane, bis(trimethoxysilyl)heptane, bis(triethoxysilyl)cyclohexane ... bis(triethoxysilyl)heptane, bis(tributoxysilylheptane, bis(triethoxysilyl)octane, bis(trimethoxysilyl)octane, bis(tributoxysilyloctane, bis(triethoxysilyl)nonane, bis(trimethoxysilyl)nonane, bis(tributoxysilylnonane, bis(triethoxysilyl)decane, bis(trimethoxysilyl)decane, bis(tributoxysilyldecane, bis(triethoxysilyl)dodecane, bis(trimethoxysilyl)dodecane, bis(tributoxysilyldodecane, bis(triethoxysilyl)tetradecane, bis(trimethoxysilyl)tetradecane, bis(tributoxysilyltetradecane, bis(triethoxysilyl)octadecane, bis(trimethoxysilyl)octadecane, bis(tributoxysilyloctadecane, and mixtures thereof.

[0038] In certain embodiments of the first and second embodiments disclosed herein, the functionalizing compound is a sulfur-containing alkoxysilane having 2 to 6 alkoxysilane groups. Preferably, according to such embodiments, the sulfur-containing alkoxysilane is selected from disulfide alkoxysilanes or tetrasulfide alkoxysilanes. Disulfide alkoxysilanes can be understood as having two sulfur atoms (single-bonded to each other), each of which is bonded to a separating alkylene group that is bonded to a silicon atom, the silicon atom having two or three alkoxy groups. Tetrasulfide alkoxysilanes can be understood as having four sulfur atoms (single-bonded to each other), each of which is bonded to a separating alkylene group that is bonded to a silicon atom, the silicon atom having two or three alkoxy groups. In certain embodiments of the first and second embodiments, the disulfide alkoxysilane is of the formula (alkoxy) a (Alkyl) 3-a Si-(CH 2 ) b -SS-(CH 2 ) b -Si(alkyl) 3-a (alkoxy) a where a is 2 or 3; b is an integer from 1 to 10, preferably 2 to 8, more preferably 2 or 3; and the alkyl in the alkoxy group is selected from alkyl of 1 to 10 carbons, preferably 1 to 6 carbons, more preferably 1 to 4 carbons. In certain embodiments of the first and second embodiments, the tetrasulfide alkoxysilane has the formula (alkoxy) d (Alkyl) 3-d Si-(CH 2 ) e SSSS-(CH 2 ) e -Si(alkyl) 3-d (alkoxy) dwhere d is 2 or 3; e is an integer from 1 to 10, preferably 2 to 8, more preferably 2 or 3; and the alkyl in the alkoxy group is selected from alkyl of 1 to 10 carbons, preferably 1 to 6 carbons, more preferably 1 to 4 carbons. Alternatively, in other embodiments, the tetrasulfide alkoxysilane has an alkoxysilane alkylene moiety at only one end of the sulfur chain (e.g., the first sulfur) and another moiety is present at the other end of the sulfur chain (e.g., the fourth sulfur) (e.g., thiocarbamoyl, benzothiazole).

[0039] In certain embodiments of the first and second embodiments disclosed herein, when the functionalizing compound is a disulfide alkoxysilane, it is selected from the group consisting of 3,3'-bis(triethoxysilylpropyl) disulfide, 3,3'-bis(trimethoxysilylpropyl) disulfide, 3,3'-bis(tributoxysilyl-propyl) disulfide, 3,3'-bis(tri-m-butoxysilyl-propyl) disulfide, 3,3'-bis(tripropoxypropyl) disulfide, 3,3'-bis(trihexoxysilylpropyl) disulfide, 2,2'-bis(di 12,12'-bis(triisopropoxysilylpropyl) disulfide, 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide, 3,3'-bis(propyldiethoxysilylpropyl) disulfide, 3,3'-bis(triisopropoxysilylpropyl) disulfide, 12,12'-bis(triisopropoxysilylpropyl) disulfide, 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide, and mixtures thereof.

[0040] In certain embodiments of the first and second embodiments disclosed herein, when the functionalizing compound is a tetrasulfide alkoxysilane, it is selected from the group consisting of bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl-benzotriazole tetrasulfide, 3-triethoxysilylpropyl benzotriazole tetrasulfide, and mixtures thereof.

[0041] In certain embodiments of the first and second embodiments disclosed herein, the functionalizing compound is a mercaptosilane compound. The mercaptosilane compound has the general formula HS-R 3 -Si(X n )(R 4 3-n wherein each X is independently a halogen or an alkoxy group (in the case of an alkoxy group, the formula OR 5 (In the formula, R 5 is C 1 ~C 6 R is an aliphatic, alicyclic, or aromatic group; 3 is C 1 ~C 4 alkylene; each R 4 is independently 1 ~C 30 Alkyl, C 7 ~C 30 Alkaril, C 5 ~C 30 Alicyclic or C 6 ~C 20aromatic; n is an integer from 1 to 4. When X is a halogen, it may be selected from the group consisting of chlorine, bromine, iodine and fluorine, preferably chlorine. In certain preferred embodiments of the first and second embodiments disclosed herein, the functionalizing compound is a mercaptosilane having the formula above, where R 3 is C 1 ~C 3 alkylene; X is an alkoxy group (C 1 ~C 6 (having a carbon portion of the formula: n is 3) 1-mercaptomethyltriethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 2-mercaptoethyltriproxysilane, 18-mercaptooctadecyldiethoxychlorosilane

[0042] In certain embodiments of the first and second embodiments disclosed herein, the functionalizing compound is a blocked mercaptosilane. The blocked mercaptosilane has the general formula BSR 6 -Si-X 3 and having a blocking group B replacing the mercapto hydrogen atom to "block" the sulfur atom from reacting with the polymer. In certain embodiments of the first and second embodiments, when the blocked mercaptosilane has the above general formula, B is a blocking group which may be in the form of an unsaturated heteroatom or carbon bonded directly to the sulfur through a single bond; 6 is C 1 ~C 6 A linear or branched alkyl chain is selected from each X independently. 1 ~C 6 Alkyl, C 1 ~C 6 Alkoxy, halogen, halogen-containing C 1 ~C 6 Alkyl and halogen-containing C 1 ~C 6The blocked mercaptosilanes suitable for use as functionalizing compounds in certain embodiments of the first and second embodiments disclosed herein include, but are not limited to, those described in U.S. Patent Nos. 6,127,468, 6,204,339, 6,528,673, 6,635,700, 6,649,684, 6,683,135, and 7,256,231. In certain embodiments of the first and second embodiments disclosed herein, when the functionalizing compound is a blocked mercaptosilane, it is selected from the group consisting of 2-triethoxysilyl-1-ethylthioacetate, 2-trimethoxysilyl-1-ethylthioacetate, 2-(methyldimethoxy-silyl)-1-ethylthioacetate, 3-trimethoxysilyl-1-propylthioacetate, triethoxysilylmethyl-thioacetate, trimethoxysilylmethylthioacetate, triisopropoxysilylmethylthioacetate, methyldiethoxysilylmethylthioacetate, methyldimethoxysilylmethylthioacetate, methyldiisopropoxysilylmethylthioacetate, dimethylethoxysilylmethylthioacetate, dimethylmethoxysilylmethylthioacetate, dimethylisopropoxysilylmethylthioacetate, 2-tri ... silyl-1-ethylthioacetate, 2-(methyldiethoxysilyl)-1-ethylthioacetate, 2-(methyldiisopropoxysilyl)-1-ethylthioacetate, 2-(dimethylethoxysilyl-1-ethylthioacetate, 2-(dimethylmethoxysilyl)-1-ethylthioacetate, 2-(dimethylisopropoxysilyl)-1-ethylthioacetate, 3-triethoxysilyl-1-propyl-thioacetate, 3-triisopropoxysilyl-1-propyl thioacetate, 3-methyldiethoxysilyl-1-propyl thioacetate, 3-methyldimethoxysilyl-1-propyl thioacetate, 3-methyldiisopropoxysilyl-1-propyl thioacetate, 1-(2-triethoxysilyl-1-ethyl)-4-thioacetylcyclohexane, 1-(2-triethoxysilyl-1-ethyl)-3-thioacetylcyclohexane,2-triethoxysilyl-5-thioacetylnorbornene, 2-triethoxysilyl-4-thioacetylnorbornene, 2-(2-triethoxysilyl-1-ethyl)-5-thioacetylnorbornene, 2-(2-triethoxy-silyl-1-ethyl)-4-thioacetylnorbornene, 1-(1-oxo-2-thia-5-triethoxysilylphenyl)benzoic acid, 6-triethoxysilyl-1-hexylthioacetate, 1-triethoxysilyl-5-hexylthioacetate, 8-triethoxysilyl-1-octylthioacetate, 1-triethoxysilyl-1-octylthioacetate, Triethoxysilyl-7-octylthioacetate, 6-triethoxysilyl-1-hexylthioacetate, 1-triethoxysilyl-5-octylthioacetate, 8-trimethoxysilyl-1-octylthioacetate, 1-trimethoxysilyl-7-octylthioacetate, 10-triethoxysilyl-1-decylthioacetate, 1-triethoxysilyl-9-decylthioacetate, 1-triethoxysilyl-2-butylthioacetate, 1-triethoxysilyl-3-butylthioacetate, 1-triethoxysilyl-3-methyl-2-butylthioacetate thioacetate, 1-triethoxysilyl-3-methyl-3-butylthioacetate, 3-trimethoxysilyl-1-propylthiooctanoate, 3-triethoxysilyl-1-propyl-1-propylthiopalmitate, 3-triethoxysilyl-1-propylthiooctanoate, 3-triethoxysilyl-1-propylthiobenzoate, 3-triethoxysilyl-1-propylthio-2-ethylhexanoate, 3-methyldiacetoxysilyl-1-propylthioacetate, 3-triacetoxysilyl-1-propylthioacetate, 2-Methyldiacetoxysilyl-1-ethylthioacetate, 2-Triacetoxysilyl-1-ethylthioacetate, 1-Methyldiacetoxysilyl-1-ethylthioacetate, 1-Triacetoxysilyl-1-ethyl-thioacetate, Tris-(3-triethoxysilyl-1-propyl)trithiophosphate, Bis-(3-triethoxysilyl-1-propyl)methyldithiophosphonate, Bis-(3-triethoxysilyl-1-propyl)ethyldithiophosphonate, 3-Triethoxysilyl-1-propyldimethylthiophosphinate,3-triethoxysilyl-1-propyl diethyl thio-phosphinate, tris-(3-triethoxysilyl-1-propyl)tetrathiophosphate, bis-(3-triethoxysilyl-1-propyl)methyl trithiophosphonate, bis-(3-triethoxysilyl-1-propyl)ethyl trithiophosphonate, 3-triethoxysilyl-1-propyl dimethyl dithiophosphinate, 3-triethoxysilyl-1-propyl diethyl dithiophosphinate, tris-(3-methyldimethoxysilyl-1-propyl)trithiophosphate, bis-(3-methyl-dimethoxysilyl-1-propyl)methyl dithiophosphonate, bis-(3-methyldimethoxysilyl-1-propyl)-ethyl dithiophosphonate, 3-methyldimethoxysilyl-1-propyl dimethyl thiophosphinate, 3-methyldimethoxysilyl-1-propyl diethyl thiophosphinate, 3-triethoxysilyl-1-propyl dimethyl dithiophosphinate The group consisting of triethoxysilyl-1-propylmethyl-thiosulfate, 3-triethoxysilyl-1-propyl methanethiosulfonate, 3-triethoxysilyl-1-propyl-ethanethiosulfonate, 3-triethoxysilyl-1-propyl benzenethiosulfonate, 3-triethoxysilyl-1-propyl toluenethiosulfonate, 3-triethoxysilyl-1-propyl naphthalenethiosulfonate, 3-triethoxysilyl-1-propyl xylylenethiosulfonate, triethoxysilylmethylmethyl thiosulfate, triethoxysilylmethyl methanethiosulfonate, triethoxysilylmethyl ethanethiosulfonate, triethoxysilylmethyl benzenethiosulfonate, triethoxysilylmethyl toluenethiosulfonate, triethoxysilylmethyl naphthalenethiosulfonate, triethoxysilylmethyl xylylenethiosulfonate, etc.,

[0043] Process for preparing modified guayule resin products As mentioned above, the second embodiment disclosed herein is directed to a process for preparing a modified guayule resin product. In general, the process of the second embodiment provides a guayule resin component that includes a mixture of argentatins with -OH groups, which can be considered as a starting product. The -OH groups of argentatins should be understood as an inherent part of the argentatin structure, and provide a site for binding to a functionalizing compound, as further discussed below. According to the process of the second embodiment, the guayule resin component is mixed with a functionalizing compound selected from an alkoxysilane, a mercaptosilane, and a blocked mercaptosilane to produce a modified guayule resin product that includes a functionalized argentatin with at least one functional group provided by the functionalizing compound.

[0044] The amount of functionalizing compound used to prepare the modified guayule resin product (or, more specifically, the functionalized argentatin therein) can vary according to the process of the second embodiment. In general, the amount of functionalizing compound can be calculated as the molar equivalent ratio of alkoxy groups from the functionalizing compound to -OH groups in the mixture of argentatin. Thus, the use of an alkoxysilane compound with relatively more alkoxy groups (e.g., 6) may require fewer moles of alkoxysilane compound to be used to produce an equivalent functionalized percentage of argentatin compared to an alkoxysilane compound with only two alkoxy groups. In certain preferred embodiments of the second embodiment, the functionalizing compound is used in an amount sufficient to provide a molar equivalent ratio of alkoxy groups from the functionalizing compound to -OH groups in the mixture of argentatin of from 1 / 1 to 6 / 1 (e.g., 1 / 1, 1.5 / 1, 2 / 1, 2.5 / 1, 3 / 1, 3.5 / 1, 4 / 1, 4.5 / 1, 5 / 1, 5.5 / 1, or 6 / 1), more preferably from 2 / 1 to 3 / 1 (e.g., 2.1 / 1, 2.2 / 1, 2.3 / 1, 2.4 / 1, 2.5 / 1, 2.6 / 1, 2.7 / 1, 2.8 / 1, 2.9 / 1, or 3 / 1).

[0045] In certain preferred embodiments of the process of the second embodiment, the use of an acid may be useful in catalyzing the reaction between the functionalizing compound and the argentatin compound. According to such embodiments, the amount of acid used may vary. In certain preferred embodiments of the process of the second embodiment, the acid is used in an amount sufficient to achieve a pH of 1 to 5 (e.g., 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5) in the mixture of the functionalizing compound and the guayule resin component. A variety of acids can be used, including, but not limited to, mineral acids. Exemplary mineral acids include hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid.

[0046] In certain preferred embodiments of the process of the second embodiment, heat is applied after the guayule resin component is mixed with the functionalizing compound. In embodiments in which an acid is added to catalyze the reaction between the functionalizing compound and the argentatin of the guayule resin component, any heat applied is preferably applied after the acid is added. In embodiments of the second embodiment in which heat is applied, the temperature to which the mixture (i.e., the mixture of the functionalizing compound, the guayule resin component, and optionally the acid) is heated can vary. In preferred embodiments, the mixture is heated to a temperature of 20-100° C. (e.g., 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100° C.).

[0047] As one skilled in the art would understand, the reaction between the functionalizing compound and the guayule resin component argentatin produces a by-product alcohol. Thus, in certain embodiments of the process of the second embodiment, the process further comprises removing the by-product alcohol from the modified guayule resin product. A variety of processes, including heat and / or vacuum, can be used to remove the by-product alcohol. EXAMPLES

[0048] The following examples illustrate certain exemplary embodiments and / or features of the embodiments of the present disclosure. The examples are provided for illustrative purposes only and should not be construed as limiting the present disclosure. Many variations to these specific examples are possible without departing from the spirit and scope of the embodiments of the present disclosure. It should be specifically understood that modified guayule resin products can be prepared using different amounts of guayule resin components (containing different amounts of argentatin), as described above, and using different amounts or types of functionalizing compounds, as described above.

[0049] Example 1 (Production of Modified Guayule Resin Product): A portion of guayule resin (guayule resin component) was mixed with a functionalizing compound in the form of n-octadecyltrimethoxysilane (97% purity, obtained from Gelest in liquid form, molecular weight 374.7 grams / mole). The guayule resin component contained about 80% by weight of argentatin and 3.8% by weight of low molecular weight rubber (measured by low molecular weight GPC). A 1 gram portion of the functionalizing compound was added to a 2 gram portion of the guayule resin component, and then 1 milliliter of water was added to promote the condensation reaction. The mixture was heated to boiling on a hot plate for about 1 hour, and then placed in a vacuum oven at 75°C for 2 hours to remove any evolved methanol. Table 1 below shows the change in the properties of the modified guayule resin product compared to the properties of the guayule resin component, which is believed to be due to the reaction of the argentatin in the guayule resin component with the functionalizing compound, causing the replacement of the methyl group by argentatin. As can be seen from the data in Table 1, the Mn, Mw and Mz values ​​of the modified guayule resin product are increased compared to the corresponding values ​​of the guayule resin components in unmodified form. Table 1 also shows the weight percentages (calculated from the areas under the peaks of selected peaks from the GPC) of the different components of the guayule resin components or modified guayule resin products. Component 1 corresponds to the oligomerization products (first peak), component 2 corresponds to the resin triglycerides and low molecular weight oligomerization products (from peaks 2 and 3, in the range of Mn from 850 to 2000 g / mol), and component 3 corresponds to the unmodified resin in the form of argentatin and guayule (from peaks 4 and 5, in the range of Mn from 400 to 850 g / mol). According to the data in Table 1, the modified guayule resin product of Example 1 has a lower amount (weight percent) of argentatin (as evidenced by the lower percentage of component 3) and a higher amount of oligomerized material (as evidenced by the higher percentage of component 1, which corresponds to the product produced from the reaction of argentatin with alkoxysilanes in the guayule resin component). Tg was measured by DSC and molecular weight values ​​were measured using GPC (using a TOSOH column, THF as the eluting solvent, and standard polystyrene).

[0050]

Table 1

[0051] Examples 2-5 (production of modified guayule resin products): A portion of the guayule resin (guayule resin component) was mixed with one of four functionalizing compounds. Example 2 utilized polydimethoxysilane (obtained from Gelest under the product name PSI-026). Example 3 utilized n-propyltrimethoxysilane (obtained from Gelest under the product name SIP 6918.0). Example 4 utilized 3-mercaptopropyltrimethoxysilane (obtained from Gelest under the product name SIM 6474.0). Example 5 utilized 4-tetraethoxysilane (obtained from Gelest under the product name SIT 7110.0). Each functionalizing compound was present in liquid form. The guayule resin component (different from the guayule resin component used in Example 1) was present in a toluene solution, and the main component of the guayule resin component was a mixture of argentatins. The guayule resin component contained approximately 76% by weight argentatin and 0.0% by weight rubber (measured by low molecular weight GPC). For each example, the respective functionalizing compound was added to a portion of the guayule resin component in toluene solution in the amount shown in Table 2 below. After the guayule resin component was mixed with the respective functionalizing compound, 2 milliliters of an acidic ethanol-water solution was added to each mixture, which was then placed on a hot plate for several hours (without stirring). (The acidic ethanol-water solution was prepared by making 10 milliliters of a 10% solution of water and ethanol and adding 1 milliliter of 6N hydrochloric acid.) The hot plate procedure was performed on a Friday and the samples were allowed to sit (at room temperature) over the weekend. On Monday morning, each sample was placed in a vacuum oven at 100° C. for 4 hours and then sent for testing. Table 3 below shows the changes in the properties of the modified guayule resin product compared to those of the guayule resin component, which are believed to be due to the reaction of argentatin in the guayule resin component with the functionalizing compound, which causes the replacement of methyl or ethyl groups by argentatin. Table 3 also shows the weight percentages (calculated from the areas under the peaks of selected peaks from GPC) of the different components of the guayule resin component or the modified guayule resin product.Component 1 corresponds to oligomerization products (first peak), component 2 corresponds to resin triglycerides and low molecular weight oligomerization products (from peaks 2 and 3, Mn range 850-2000 g / mol), and component 3 corresponds to unmodified resin in the form of argentatin and guayule (from peaks 4, 5, and 6, Mn range 400-850 g / mol). According to the data in Table 3, each of the modified guayule resin products of Examples 2-5 has a lower amount (weight percent) of argentatin (as evidenced by the lower percentage of component 3) and a higher amount of oligomerization material (as evidenced by the higher percentage of component 1, which corresponds to the product produced from the reaction of argentatin with the functionalizing compound in the guayule resin component). While only Example 4 shows an increase in Mn, Mw, and Mz, the fact that the percentage of component 3 decreases for each of Examples 2-5 and the amount of component 1 increases for each of Examples 2-5 indicates that a reaction has occurred between argentatin and the functionalizing compound in the guayule resin component. Tg was measured by DSC and molecular weight values ​​were measured using GPC (using a TSOH column, THF as the eluting solvent, and standard polystyrene).

[0052] [Table 2]

[0053] [Table 3]

[0054] The present application discloses several numerical range limits that support any range within the disclosed numerical ranges, even if no explicit range limit is literally stated in the specification, since the compositions and methods disclosed herein can be practiced throughout the disclosed numerical ranges. With respect to the use of virtually any plural or singular term herein, one of ordinary skill in the art can substitute plural for singular or singular for plural as appropriate to the situation or application. Various singular or plural substitutions may be explicitly stated herein for the sake of brevity.

[0055] In general, those skilled in the art will understand that the terms used in this specification, and in particular in the appended claims, are generally intended to be "open" terms. For example, the term "including" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," and the term "including" should be interpreted as "including but not limited to." Furthermore, those skilled in the art will understand that if a specific number is intended in a prefaced claim recitation, such intent shall be expressly recited in the claim, and in the absence of such recitation, no such intent exists. For example, as an aid to understanding, the following appended claims may include the use of the preface phrases "at least one" and "one or more" to preface the claim recitation. However, the use of such phrases should not be construed as meaning that the preface of a claim recitation with the indefinite article "a" or "an" limits any particular claim that includes the claim recitation so prefaced to an invention that contains only one such recitation, even if the same claim includes the prefaced phrase "one or more" or "at least one" and an indefinite article such as "a" or "an" (e.g., "a" or "an" should typically be construed to mean "at least one" or "one or more"), and the same is true for the use of definite articles used to preface a claim recitation. In addition, even if a particular number is explicitly recited in a prefaced claim recitation, those skilled in the art will understand that such a recitation should typically be construed to mean at least the recited number (e.g., the explicit recitation "two recitations" without any other modifier typically means at least two recitations, or more than two recitations). Furthermore, when a conventional expression similar to "at least one of A, B, and C, etc." is used, such a configuration is generally intended in the sense that one of ordinary skill in the art would understand the conventional expression (e.g., "a system having at least one of A, B, and C" may include, but is not limited to, a system having only A, only B, only C, both A and B, both A and C, both B and C, and / or both A, B, and C, etc.).Moreover, one skilled in the art will appreciate that virtually any disjunctive word or phrase indicating two or more alternative terms, whether in the specification, claims, or drawings, should be understood to contemplate the possibility of including one of those terms, either of those terms, or both of those terms. For example, the phrase "A or B" will be understood to include the possibility of "A" or "B" or "A and B." All references, including but not limited to patents, patent applications, and non-patent literature, are incorporated herein by reference in their entirety. While various aspects and embodiments of the compositions and methods have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for illustrative purposes only and are not intended to limit the true scope and spirit of the appended claims. [1] 1. A modified guayule resin product comprising a mixture of argentatin having at least one functional group, said at least one functional group being provided by a functionalizing compound selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes. [2] The modified guayule resin product according to [1] above, wherein the functionalizing compound is a sulfur-containing alkoxysilane, preferably selected from disulfide alkoxysilanes or tetrasulfide alkoxysilanes. [3] The functionalizing compound is a disulfide alkoxysilane compound, preferably 3,3'-bis(triethoxysilylpropyl) disulfide, 3,3'-bis(trimethoxysilylpropyl) disulfide, 3,3'-bis(tributoxysilyl-propyl) disulfide, 3,3'-bis(tri-m-butoxysilyl-propyl) disulfide, 3,3'-bis(tripropoxypropyl) disulfide, 3,3'-bis(trihexoxysilylpropyl) disulfide, 2,2'-bis(dimethylmethoxysilylethyl) disulfide, 3,3' 3,3'-bis(diphenylcyclohexoxysilylpropyl) disulfide, 3,3'-bis(ethyl-di-sec-butoxysilylpropyl) disulfide, 3,3'-bis(propyldiethoxysilylpropyl) disulfide, 3,3'-bis(triisopropoxysilylpropyl) disulfide, 12,12'-bis(triisopropoxysilylpropyl) disulfide, 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide, and combinations thereof. [4] The functionalizing compound is (a) a non-sulfur-containing alkoxysilane having formula (I): R 1 (4-n) -Si(OR 2 ) n (I) (wherein n=2, 3, or 4; each R 1 are independently selected from hydrocarbyl groups having 1 to 24 carbons, preferably alkyl or cycloalkyl groups having 3 to 18 carbons, or aryl groups having 6 to 18 carbons; R 2 is an alkyl group having 1 to 10 carbons, preferably 1 to 6 carbons, and more preferably 1 to 3 carbons; or (b) non-sulfur-containing bisalkoxysilanes having 4 to 6 alkoxy groups The modified guayule resin product according to [1] above, wherein the non-sulfur-containing alkoxysilane is selected from the following: [5] The functionalizing compound has the formula (I), where n=3 and R 1 is selected from alkyl groups having 6 to 24 carbons, preferably 12 to 20 carbons; R 2 The modified guayule resin product according to [4] above, wherein is methyl or ethyl. [6] The modified guayule resin product according to [5], wherein the functionalizing compound comprises at least one of octadecyltrimethoxysilane, octadecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, or hexadecyltriethoxysilane. [7] The modified guayule resin product according to [1], wherein the functionalizing compound is a mercaptosilane. [8] The modified guayule resin product according to [1] above, wherein the functionalizing compound is a blocked mercaptosilane. [9] The modified guayule resin product according to any one of the above [1] to [8], which has a Tg of -70 to 100°C.

[10] The modified guayule resin product according to [9] above, having a Tg of -60 to 0°C.

[11] The modified guayule resin product according to the above [9], having a Tg of 1 to 100°C, preferably 30 to 90°C, more preferably 40 to 90°C.

[12] The modified guayule resin product according to any one of the above [1] to

[11] , wherein the modified guayule resin has an Mn of 1600 to 5000 g / mol and / or an Mw of 2000 to 10000 g / mol.

[13] The modified guayule resin product according to any one of the above [1] to

[12] , wherein the mixture of argentatins has at least 50% by weight, preferably 60 to 90% by weight, of hydrogen atoms from -OH groups of the mixture of argentatins replaced with the at least one functional group.

[14] The modified guayule resin product according to any one of the above [1] to

[13] , wherein less than 10% by weight, preferably less than 5% by weight, of guayule rubber is present in the modified guayule resin product.

[15] The modified guayule resin product according to any one of the above [1] to

[14] , wherein the mixture of functionalized argentatin constitutes at least 40% by weight of the modified guayule resin product, preferably the majority by weight of the modified guayule resin product, more preferably at least 60% by weight or 60 to 95% by weight of the modified guayule resin product.

[16] The modified guayule resin product according to any one of the above [1] to

[14] , wherein the mixture of modified argentatin is the major component by weight of the modified guayule resin product.

[17] 1. A process for preparing a modified guayule resin product comprising: a. providing a guayule resin component comprising a mixture of argentatins having -OH groups; b. mixing the guayule resin component with a functionalizing compound selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes; c. forming a modified guayule resin product comprising a functionalized argentatin having at least one functional group provided by said functionalizing compound; and The process includes:

[18] 18. The process of claim 17, wherein the mixture of argentatin is the majority by weight of the guayule resin component.

[19] 18. The process according to claim 17, wherein the mixture of argentatin constitutes at least 40% by weight of the guayule resin component, preferably the majority by weight of the guayule resin component, more preferably at least 60% by weight or between 60 and 90% by weight of the guayule resin component.

[20] The process according to any one of

[17] to

[19] above, wherein the functionalizing compound is used in an amount sufficient to provide a molar equivalent ratio of alkoxy groups from the functionalizing compound to -OH groups in the mixture of argentatin in a ratio of 1 / 1 to 6 / 1, preferably 2 / 1 to 3 / 1.

[21] The process according to any one of

[17] to

[20] above, wherein (b) comprises adding an acid, preferably in an amount sufficient to achieve a pH of 1 to 5.

[22] The process according to any one of the above

[17] to

[21] , wherein after mixing the guayule resin component with the functionalizing compound, heat is applied, preferably to a temperature of 20 to 100°C.

[23] The process according to any one of

[17] to

[22] above, wherein (c) comprises the production of a by-product alcohol formed from an alkoxy group of the alkoxysilane, and the process further comprises removing the by-product alcohol, preferably by use of heat and / or vacuum.

[24] The process according to any one of

[17] to

[23] , wherein the modified guayule resin product produced in (c) is as defined in any one of claims 2 to 14.

Claims

1. A mixture of argentatins having at least one functional group, said at least one functional group being provided by a functionalizing compound selected from alkoxysilanes, mercaptosilanes, and blocked mercaptosilanes; A modified guayule resin product, wherein said mixture of argentatins having at least one functional group constitutes at least 40% by weight of the modified guayule resin product.

2. 2. The modified guayule resin product of claim 1 having a Tg of from -70 to 100°C.

3. 2. The modified guayule resin product of claim 1 having a Tg of from -10 to 100°C.

4. 2. The modified guayule resin product of claim 1 having a Tg of 30 to 90°C.

5. The modified guayule resin product of any one of claims 1 to 4, wherein less than 10% by weight of guayule rubber is present in the modified guayule resin product.

6. A process for preparing the modified guayule resin product according to any one of claims 1 to 5, comprising the steps of: a. providing a guayule resin component comprising a mixture of argentatins having —OH groups; b. mixing the guayule resin component with a functionalizing compound selected from an alkoxysilane, a mercaptosilane, and a blocked mercaptosilane; c. Producing a modified guayule resin product comprising a functionalized argentatin having at least one functional group provided by said functionalizing compound; The process includes:

7. 7. The process of claim 6, wherein (b) comprises adding an acid, heat is applied after mixing the guayule resin component with a functionalizing compound in (b), and (c) comprises producing a by-product alcohol produced from an alkoxy group of the alkoxysilane, the process further comprising removing the by-product alcohol.

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