Novolak resin composition and method of making the same

Abstract

The present disclosure is directed to a novolak resin composition comprising a modified novolak resin and a method of preparing the same. The modified novolak resin can be prepared from a hydrocarbylphenol, a vinyl compound modifying agent and / or a dimer thereof, and an aldehyde and / or ketone. The present disclosure is also directed to a rubber composition including the novolak resin composition comprising the modified novolak resin.

Description

NOVOLAK RESIN COMPOSITION AND METHOD OF MAKING THE SAMECross-Reference to Related Application

[0001] The present application claims filing benefit of U.S. Provisional Patent Application No. 63 / 509,542 having a filing date of June 22, 2023, which is hereby incorporated by reference in its entirety.Background

[0002] Rubber products can be made from natural rubber, synthetic rubber, or blends thereof. In certain instances, these rubber products can be made of several rubber layers, each with the same or different chemical composition.During manufacture, it may be desirable for a respective layer to adhere to one or more adjacent layers, particularly when in a pre-vulcanized state. In this regard, it may be desired for a rubber or rubber mixture to have a particular tack - which may generally be defined as a force required to pull apart two pre-vulcanized rubber or rubber mixtures which have been pressed together under certain defined conditions. While natural rubber mixtures may generally have good tackiness, mixtures of synthetic rubbers may be less tacky or possess no tackiness at all. As a result, a tackifier may be added to the rubber or rubber mixture to increase the tack.

[0003] Novolak resins may be used as tackifiers in a large variety of rubber compositions. Generally, these resins have a repeating structure of phenolic units obtained by reacting phenolic compounds with aldehydes in the presence of an acid catalyst. Differing in chemical structure, a variety of phenolic novolak resins have been combined with rubber formulations as tackifier resins. In addition, novolak resins may be modified post-synthesis to improve the tackiness of the resin. However, such synthesis may require additional processing steps and may further complicate the method of making the modified novolak resin.

[0004] As a result, there is a desire to provide an improved method of synthesizing a modified novolak resin, in particular one having improved purity.Summary

[0005] In accordance with one embodiment of the present invention, a method of making a novolak resin composition comprising a modified novolakresin is disclosed. The method comprises: providing a mixture comprising a hydrocarbylphenol and a vinyl compound modified hydrocarbylphenol and reacting an aldehyde and / or ketone with the hydrocarbylphenol in the presence of the vinyl compound modified hydrocarbylphenol to form the modified novolak resin wherein at least one end of the modified novolak resin is formed from the vinyl compound modified hydrocarbylphenol.

[0006] In accordance with another embodiment of the present invention, a method of making a novolak resin composition comprising a modified novolak resin is disclosed. The method comprises: providing a mixture comprising a hydrocarbylphenol and a vinyl compound modifying agent and / or a dimer thereof; reacting a portion of the hydrocarbylphenol and the vinyl compound modifying agent and / or a dimer thereof to form a vinyl compound modified hydrocarbylphenol; and reacting an aldehyde and / or ketone with the hydrocarbylphenol in the presence of the vinyl compound modified hydrocarbylphenol to form the modified novolak resin wherein at least one end of the modified novolak resin is formed from the vinyl compound modified hydrocarbylphenol.

[0007] In accordance with another embodiment of the present invention, a novolak resin composition comprising a modified novolak resin is disclosed. The novolak resin composition comprising a modified novolak resin is formed by a method comprising: providing a mixture comprising a hydrocarbylphenol and a vinyl compound modified hydrocarbylphenol and reacting an aldehyde and / or ketone with the hydrocarbylphenol in the presence of the vinyl compound modified hydrocarbylphenol to form the modified novolak resin wherein at least one end of the modified novolak resin is formed from the vinyl compound modified hydrocarbylphenol.

[0008] In accordance with another embodiment of the present invention, a rubber composition is disclosed. The rubber composition comprises a rubber and the aforementioned novolak resin composition.

[0009] In accordance with another embodiment of the present invention, a novolak resin composition comprising a modified novolak resin is disclosed. The novolak resin composition comprising a modified novolak resin is formed by a method comprising: providing a mixture comprising a hydrocarbylphenol and a vinyl compound modifying agent and / or a dimer thereof; reacting a portion of thehydrocarbylphenol and the vinyl compound modifying agent and / or a dimer thereof to form a vinyl compound modified hydrocarbylphenol; and reacting an aldehyde and / or ketone with the hydrocarbylphenol in the presence of the vinyl compound modified hydrocarbylphenol to form the modified novolak resin wherein at least one end of the modified novolak resin is formed from the vinyl compound modified hydrocarbylphenol.

[0010] In accordance with another embodiment of the present invention, a rubber composition is disclosed. The rubber composition comprises a rubber and the aforementioned novolak resin composition.Definitions

[0011] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present disclosure.

[0012] “About” means within 5% of the disclosed value.

[0013] “Alkenyl” refers to a linear or branched hydrocarbyl group having from 2 to 10 carbon atoms and in some embodiments from 2 to 6 carbon atoms or 2 to 4 carbon atoms and having at least 1 site of vinyl unsaturation (>C=C<). For example, “Cq-Cr alkenyl” refers to alkenyl groups having from q to r carbon atoms and is meant to include for example, ethenyl, propenyl, 1 ,3-butadienyl, and so forth.

[0014] “Alkyl” refers to straight chain, branched chain, or cyclic monovalent saturated aliphatic hydrocarbyl groups and “Cq-Cr alkyl” refers to alkyl groups having from q to r carbon atoms. This term includes, by way of example, straight chain, branched chain, or cyclic hydrocarbyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosanyl, henicosanyl, docosanyl, tricosanyl, tetracosanyl, pentacosanyl, hexacosanyl, heptacosanyl, octacosanyl, and the like.

[0015] “Alkoxy” refers to a straight or branched alkoxy group having from 1 to 6 carbon atoms unless specified otherwise. For example, “Cq-Cr alkoxy” means a straight or branched alkoxy group containing from q to r carbon atoms, such as from 1 to 6 carbon atoms. Examples of “alkoxy” as used herein include, but are notlimited to, methoxy, ethoxy, prop-1 -oxy, prop-2-oxy, but-1-oxy, but-2-oxy, 2- methylprop-1-oxy, 2-methylprop-2-oxy, pentoxy and hexyloxy.

[0016] “Alkynyl” refers to a linear monovalent hydrocarbon radical or a branched monovalent hydrocarbon radical containing at least one triple bond. The term “alkynyl” is also meant to include those hydrocarbyl groups having one triple bond and one double bond. For example, C2-C6 alkynyl is meant to include ethynyl, propynyl, and so forth.

[0017] “Amino” refers to the group NH2.

[0018] “Aryl” refers to a 5- or 6- membered aromatic ring, for example phenyl, or a 7 to 12 membered bicyclic ring system where at least one of the rings is aromatic, for example naphthyl. An aryl group may be optionally substituted by one or more substituents, for example up to 4, 3 or 2 substituents. Preferably the aryl group is phenyl.

[0019] “Carbonyl” refers to the divalent group -C(O)- which is equivalent to - C(=O)-.

[0020] “Carboxyl” or “carboxy” refers to -COOH or salts thereof.

[0001] “Cycloalkenyl” refers to a partially saturated cycloalkyl ring having at least one site of >C=C< ring unsaturation.

[0021] “Cycloalkyl” refers to a saturated cyclic group containing 3 to 6 carbon ring-atoms (unless otherwise specified). Examples include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0022] “Halo” or “halogen” refers to a fluorine (fluoro, F), chlorine (chloro, Cl), bromine (bromo, Br) or iodine (iodo, I).

[0023] “Hydrocarbyl” refers to a hydrocarbon substituent including aliphatic (straight-chain and branched-chain) and cyclic, such as alicyclic, aromatic, and cyclic terpenes. The hydrocarbyl group may be substituted with common functional groups including, but not limited to, hydroxyl groups, amino groups, carboxylic groups, halogens, thiol groups, disulfide groups, etc.

[0024] “Heterocyclyl” refers to an aromatic or nonaromatic five or six membered ring which contains from 1 to 4 heteroatoms selected from nitrogen, oxygen, or sulfur and is unsubstituted or substituted by, for example, up to three substituents, preferably one or two substituents. Examples of 5-membered heterocyclyl groups include furyl, dioxalanyi, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, triazinyl, isothiazolyl, isoxazolyl, thiophenyl,pyrazoiyl or tetrazolyl. Examples of 6-membered heterocyclyl groups are pyridyl, pyridazinyl, pyrlmidinyl, pyrazinyl, triazinyl or tetrazinyLDetailed Description

[0025] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present invention.

[0026] In general, the present disclosure is directed to a novolak resin composition and a method of making the same. The novolak resin composition includes one or more modified novolak resins as defined herein. Without intending to be limited by theory, the modified novolak resin may be able to provide a desired tack for particular applications, such as for rubber applications.Furthermore, the method as disclosed herein may allow for the synthesis of the novolak resin composition and modified novolak resin utilizing a relatively simpler process which may not require a post-synthesis modification of a novolak resin.

[0027] Furthermore, the present inventors have discovered that utilizing the method as disclosed herein can provide a novolak resin composition and modified novolak resin with a relatively low amount of substances of very high concern (also referred to as SVHCs). These substances may generally include C4-C12 alkyl substituted phenols, para-substituted phenols, or a mixture thereof. The SVHCs can be monomer inputs into the processes described herein.

[0028] The substances of very high concern may be present in an amount of about 4 wt.% or less, such as about 3.5 wt.% or less, such as about 3 wt.% or less, such as about 2.5 wt.% or less, such as about 2 wt.% or less, such as about 1 .8 wt.% or less, such as about 1.6 wt.% or less, such as about 1.4 wt.% or less, such as about 1.2 wt.% or less, such as about 1 wt.% or less, such as about 0.9 wt.% or less, such as about 0.8 wt.% or less, such as about 0.7 wt.% or less, such as about 0.6 wt.% or less, such as about 0.5 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less. The substances of very high concern may be present in an amount of 0 wt.% or more, such as more than 0 wt.%, such as about 0.001 wt.% or more, such as about 0.005 wt.% or more, such as about 0.01 wt.% or more, such as about 0.03 wt.% or more, such as about 0.05 wt.% or more, such as about 0.08 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more,such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more. In one embodiment, the aforementioned weight percentages may be based on the weight of the novolak resin composition. In another embodiment, the aforementioned weight percentages may be based on the weight of the one or more modified novolak resins.

[0029] Similarly, the method as disclosed herein may also allow for a composition and resulting material having a relatively low monomer concentration of hydrocarbylphenol. For instance, hydrocarbylphenol(s) may be present in an amount of about 4 wt.% or less, such as about 3.5 wt.% or less, such as about 3 wt.% or less, such as about 2.5 wt.% or less, such as about 2 wt.% or less, such as about 1.8 wt.% or less, such as about 1 .6 wt.% or less, such as about 1 .4 wt.% or less, such as about 1 .2 wt.% or less, such as about 1 wt.% or less, such as about 0.9 wt.% or less, such as about 0.8 wt.% or less, such as about 0.7 wt.% or less, such as about 0.6 wt.% or less, such as about 0.5 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less. In addition, hydrocarbylphenol(s) may be present in an amount of 0 wt.% or more, such as more than 0 wt.%, such as about 0.001 wt.% or more, such as about 0.005 wt.% or more, such as about 0.01 wt.% or more, such as about 0.03 wt.% or more, such as about 0.05 wt.% or more, such as about 0.08 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more. In one embodiment, the aforementioned weight percentages may be based on the weight of the novolak resin composition. In another embodiment, the aforementioned weight percentages may be based on the weight of the modified novolak resin.

[0030] Generally, the method includes providing a hydrocarbylphenol and a vinyl compound modified hydrocarbylphenol. In this regard with respect to the latter, the vinyl compound modified hydrocarbylphenol may include a residue of a vinyl compound modifying agent and / or a dimer-based residue of a vinyl compound modifying agent as defined herein. In one embodiment, the vinyl compound modified hydrocarbylphenol may be prepared in advance of providing with the hydrocarbylphenol. For instance, the residue of a vinyl compound modifying agent or a dimer-based residue of a vinyl compound modifying agent may already be provided on the hydrocarbylphenol. In another embodiment, thevinyl compound modified hydrocarbylphenol may be prepared in situ. For instance, a vinyl compound modifying agent and / or a dimer thereof as defined herein may be provided to react with at least a portion of the hydrocarbylphenol. In a further embodiment, the vinyl compound modified hydrocarbylphenol may be prepared in advance and provided in addition to preparing at least some of the vinyl compound modified hydrocarbylphenol in situ.

[0031] The method may also comprise providing an aldehyde and / or ketone. For instance, such aldehyde and / or ketone may react with the hydrocarbylphenol in the presence of the vinyl compound modified hydrocarbylphenol to form the modified novolak resin. Furthermore, the vinyl compound modified hydrocarbylphenol may also react to form one or both end caps of the modified novolak resin.

[0032] In one embodiment, the respective components may be provided together. In another embodiment, the hydrocarbylphenol and the vinyl compound modified hydrocarbylphenol may first be provided and thereafter the aldehyde and / or ketone may be provided. In another embodiment, the hydrocarbylphenol and the vinyl compound modifying agent may first be provided and thereafter the aldehyde and / or ketone may be provided. For instance, at least a portion of the hydrocarbylphenol may be allowed to react with the vinyl compound modifying agent. Such reaction may result in the formation of the vinyl compound modified hydrocarbylphenol. In this regard, a resulting mixture may include the hydrocarbylphenol and the vinyl compound modified hydrocarbylphenol. To the extent any vinyl compound modifying agent has not reacted, the resulting mixture may also include such vinyl compound modifying agent. As indicated, the aldehyde and / or ketone may be introduced after the introduction or synthesis of at least some vinyl compound modified hydrocarbylphenol. In this regard, a resulting mixture may also include the aldehyde and / or ketone. Upon reacting the components, the resulting mixture may include a modified novolak resin along with any unreacted components, such as the hydrocarbylphenol, the vinyl compound modified hydrocarbylphenol, the vinyl compound modifying agent, and / or the aldehyde and / or ketone.

[0033] The vinyl compound modified hydrocarbylphenol may be utilized to cap at least one end of the modified novolak resin. In one embodiment, the vinyl compound modified hydrocarbylphenol may be utilized to cap both ends of themodified novolak resin. In this regard, the modified novolak resin may have a structural formulawhereinRi is an optionally substituted hydrocarbyl group;V is a vinyl compound modifying agent residue or a dimer-based residue of a vinyl compound modifying agent;W is a vinyl compound modifying agent residue or a dimer-based residue of a vinyl compound modifying agent; n is 1 or more; z is from 0 to 1 ; and x is from 0 to 1 , wherein at least one of z or x is 1.

[0034] As one example wherein V and W are a vinyl compound modifying agent residue, in particular of a-methylstyrene, the modified novolak resin may have the following structural formula (la):whereinRi is as defined above; and n is as defined above.

[0035] As another example wherein one of V and W, such as V, is a vinyl compound modifying agent residue, in particular of a-methylstyrene, and wherein one of V and W, such as W, is a dimer-based residue of a vinyl compound modifying agent, in particular of a-methylstyrene, the modified novolak resin may have the following structural formula (lb):whereinRi is as defined above; and n is as defined above.

[0036] As a further example wherein V and W are a dimer-based residue of a vinyl compound modifying agent, in particular of a-methylstyrene, the modified novolak resin may have the following structural formula (Ic):whereinRi is as defined above; and n is as defined above.

[0037] In the above formulae, n is 1 or more. In this regard, n may be from 1 to 100. For instance, n may be 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more, such as 10 or more, such as 15 or more, such as 20 or more, such as 25 or more, such as 30 or more, such as 40 or more, such as 50 or more. In addition, n may be 100 or less, such as 80 or less, 60 or less, such as 40 or less, such as 20 or less, such as 15 or less, such as 12 or less, such as 10 or less, such as 9 or less, such as 8 or less, such as 7 or less, such as 6 or less, such as 5 or less, such as 4 or less.

[0038] Also in the above formula, z is from 0 to 1 . In one embodiment, z is 0. In another embodiment, z is 1 . Similarly, x is from 0 to 1. In one embodiment, x is 0. In another embodiment, x is 1 . Regardless, at least one of z and x is 1 .

[0039] In one embodiment, both z and x may be the same. For instance, both z and x may be 1 . In a further embodiment, both z and x may be different. For instance, z may be 0 while x may be 1. In another embodiment, z may be 1 while x may be 0.

[0040] In forming the modified novolak resin as disclosed herein and as indicated above, the method utilizes a hydrocarbylphenol. In general, it is known in the art that the phenyl ring of phenols may be derivatized with aldehydes and / or ketones only by reactions at the ortho- and para- positions to the hydroxyl group. In this regard, the meta-position on the phenyl ring is not reactive. In the preparation of novolak resins, polymerization occurs at the two ortho- positions and one para-position. The modified novolak resins are prepared from one or more phenols having one hydrocarbyl substituent in one ortho- or in the paraposition to the hydroxyl group. In one particular embodiment, the modified novolak resins are prepared from one or more phenols having one hydrocarbyl substituent in the para-position to the hydroxyl group. As a result, this leaves only two ring positions, either two ortho-positions (para-hydrocarbyl substitution) or one orthoposition and one para-position (ortho-hydrocarbyl substitution), available for polymerization. The resulting modified novolak resin then is a “linear” resin.Linear novolak resins to be used may be prepared from ortho-hydrocarbylphenols, para-hydrocarbylphenols, or a mixture of ortho-hydrocarbylphenols and para- hydrocarbylphenols. In one embodiment, linear novolak resins may be prepared from para-hydrocarbylphenols.

[0041] Accordingly, the hydrocarbylphenol has a hydrocarbyl group corresponding to Ri in structural formulae above. The hydrocarbyl group may be a Ci-Cso hydrocarbyl group. For instance, the hydrocarbyl group may have 1 or more, such as 2 or more, such as 3 or more, such as 4 or more, such as 5 or more, such as 6 or more, such as 7 or more, such as 8 or more, such as 9 or more, such as 10 or more, such as 12 or more, such as 14 or more, such as 18 or more, such as 20 or more carbon atoms. The hydrocarbyl group may have 60 or less, such as 50 or less, such as 40 or less, such as 30 or less, such as 26 or less, such as 22 or less, such as 20 or less, such as 16 or less, such as 14 or less, such as 12 or less, such as 10 or less, such as 9 or less, such as 8 or less, such as 7 or less, such as 6 or less, such as 5 or less carbon atoms.

[0042] In one embodiment, the hydrocarbyl group may be an aliphatic group. In particular, the hydrocarbyl group may be an alkyl group. For instance, the hydrocarbyl group may be a butyl group and / or an octyl group. In particular, the hydrocarbyl group may be a t-butyl group and / or a t-octyl group. In one embodiment, the hydrocarbyl group may be a t-butyl group. In another embodiment, the hydrocarbyl group may be a t-octyl group.

[0043] In one embodiment, the hydrocarbyl group may be substituted with a functional group. For instance, the functional group may include, but is not limited to, a hydroxyl group, an amino group, a carboxyl group, a halogen, a thiol group, a disulfide group, etc., or a combination thereof. In addition, more than one of the aforementioned functional groups may be utilized as substituent groups. The functional group should generally not impair the tackifying properties of the modified novolak resin, the resulting novolak resin composition, and / or the resulting application (e.g., rubber composition). In general, the functional group may be provided to add beneficial properties to the resin for manufacturing purposes, for increased tack, or for improving the properties for a general application (e g., of a rubber composition to which it is added). However, in another embodiment, the hydrocarbyl group may not be functionalized (or substituted).

[0044] The hydrocarbylphenol may have the following structural formula (II):whereinRi is as defined above.

[0045] The hydrocarbylphenol may also include a mixture of hydrocarbylphenols satisfying the structure for formula (II) wherein Ri may be different in each hydrocarbylphenol. For instance, each Ri may have a different length and / or configuration (e.g., straight vs. branched). Such a mixture of hydrocarbylphenols may be utilized in forming the novolak resin disclosed herein. Accordingly, the resulting novolak resins disclosed herein having a hydrocarbylsubstituent may have some variation within the Ri group within a particular novolak resin. In this regard, in one embodiment for example, Ri may include Cs alkyls. In another embodiment for example, Ri may include a combination of a Cs alkyl and C4 and / or C12 alkyls, such as a combination of a Cs alkyl and a C4 alkyl.

[0046] Examples of hydrocarbylphenols include, but are not limited to, butylphenol (such as p-tert-butyl phenol (PTBP)), octylphenol (such as p- octylphenol (POP), p-tert-octyl phenol (PTOP)), nonylphenol, tetracosanylphenol, pentacosanylphenol, hexacosanylphenol, heptacosanylphenol, octacosanylphenol, etc., as well as mixtures thereof. In one particular embodiment, the hydrocarbylphenol includes butylphenol (such as p-tert-butyl phenol (PTBP)), octylphenol (such as p-octylphenol (POP), p-tert-octylphenol (PTOP)), or a mixture thereof. Particularly, the hydrocarbylphenol includes p-tert-butyl phenol (PTBP), p- octylphenol (POP), p-tert-octylphenol (PTOP), or a mixture thereof. In one particular embodiment, the hydrocarbylphenol includes p-tert-octylphenol (PTOP). In another particular embodiment, the hydrocarbylphenol includes p-octylphenol (POP).

[0047] As indicated above, the hydrocarbylphenol may be provided with a vinyl compound modified hydrocarbylphenol. The vinyl compound modified hydrocarbylphenol may have the structural formula (Illa) or (111 b):whereinRi is as defined above;V is as defined above;W is as defined above; z is as defined above; and x is as defined above, wherein at least one of z or x is 1 .

[0048] Such compounds of formula (Illa) and / or (lllb) may be provided with the hydrocarbylphenol such that they are not synthesized in situ in one embodiment. In another embodiment, such compounds of formula (Illa) and / or(Illb) may be prepared in situ by reacting at least some of the hydrocarbylphenol with a vinyl compound modifying agent and / or a dimer thereof as defined herein.

[0049] As indicated in structural formula (II) above, the hydrocarbylphenol may include one hydrocarbyl group. In some embodiments, the reaction mixture may also further include a hydrocarbylphenol including two hydrocarbyl groups. For instance, such groups may be at the para position to the hydroxyl and one ortho position to the hydroxyl. When present, they may also form one or more of the end caps of the modified novolak resin. When forming an end cap, it may be connected via a methylene bridge (e.g., formed from formaldehyde). Such a hydrocarbyl group may have structural formula (IV):whereinRi is as defined above; andR? is an optionally substituted hydrocarbyl group.

[0050] In general, the R7 hydrocarbyl group may be any hydrocarbyl group as indicated above with respect to R1. In addition, in one embodiment, the R7 hydrocarbyl group may not be substituted. Furthermore, the R7 hydrocarbyl group may be the same as the R1 hydrocarbyl group in one embodiment. In another embodiment, the R7 hydrocarbyl group may be different from the R1 hydrocarbyl group.

[0051] Generally, the hydrocarbylphenols of formula (IV) include dialkylated phenols. These may include, but are not limited to, 2,4-xylenol, 2,4-di-tert- butylphenol, 2,4-di-tert-octylphenol, ortho-cumyl-octylphenol, etc. as well as mixtures thereof.

[0052] The hydrocarbylphenol of formula (IV) may be provided for the synthesis in a particular amount. For instance, if present, it may be present in an amount of less than 30 mol.%, such as 25 mol.% or less, such as 23 mol.% or less, such as 20 mol.% or less, such as 18 mol.% or less, such as 15 mol.% or less, such as 12 mol.% or less, such as 10 mol.% or less, such as 9 mol.% or less,such as 8 mol.% or less, such as 7 mol.% or less, such as 6 mol.% or less, such as 5 mol.% or less, such as 4 mol.% or less, such as 3 mol.% or less, such as 2 mol.% or less, such as 1 mol.% or less based on the total moles of hydrocarbylphenols.

[0053] In this regard, the hydrocarbylphenol of formula (II) may also be provided for the synthesis in a particular amount. For instance, it may be present in an amount of 20 mol.% or more, such as 30 mol.% or more, such as 40 mol.% or more, such as 50 mol.% or more, such as 60 mol.% or more, such as 70 mol.% or more, such as 80 mol.% or more, such as 90 mol.% or more, such as 92 mol.% or more, such as 95 mol.% or more, such as 97 mol.% or more, such as 98 mol.% or more, such as 99 mol.% or more based on the total moles of hydrocarbylphenols.

[0054] As indicated in structural formula (I) above, V and W are independently a vinyl compound modifying agent residue or a dimer-based residue of a vinyl compound modifying agent. In this regard, in one embodiment, they are independently the residue of a vinyl compound modifying agent as defined herein upon reacting with a hydrocarbylphenol as defined herein. For instance, upon reaction with the hydrocarbylphenol and conversion of the unsaturated carboncarbon bond to a saturated bond with the hydrocarbylphenol, the residue of the vinyl compound modifying agent is noted by V and W in the structural formula. Similarly, V and / or W ean independently be a dimer-based residue of a vinyl compound modifying agent. For instance, the vinyl compound modifying agent may be capable of forming a dimer and such dimer may be utilized as V and / or W. In particular, the dimer may first be formed and the subsequent dimer-based residue formed as V and / or W on the hydrocarbylphenol. Alternatively, the vinyl compound modifying agent residue may first be present on the hydrocarbylphenol and thereafter a subsequent vinyl compound modifying agent, particularly of the same species, may react with the vinyl compound modifying agent residue to form the dimer-based residue.

[0055] As indicated, in order to form the vinyl modified hydrocarbylphenol, at least some of the hydrocarbylphenol is reacted with a vinyl compound modifying agent and / or a dimer thereof. In this regard, the vinyl compound modifying agent or a dimer thereof may be a compound having an unsaturated carbon-carbon bond. In particular, the vinyl compound modifying agent or a dimer thereof may bea vinyl compound having only one unsaturated carbon-carbon bond. Such unsaturated carbon-carbon bond may react with the hydrocarbylphenol for purposes of modifying the hydrocarbylphenol to form a vinyl compound modified hydrocarbylphenol.

[0056] Generally, any vinyl compound modifying agent and / or a dimer thereof can be used to modify the hydrocarbylphenol to provide a vinyl compound modified hydrocarbylphenol and resulting modified novolak resin. In general, the term “vinyl compound” means a compound having a vinyl group (CH2=CR — ) wherein R is hydrogen or a substituent. Any compound containing a vinyl group that may react with a hydrocarbylphenol as disclosed herein may be utilized as a vinyl compound for making the vinyl compound modified hydrocarbylphenol and / or modified novolak resin as disclosed herein. In certain embodiments, the vinyl compound has the following structural formula (V):wherein each of R2, R3, R4, and Rs is independently H, an organyl group, or a functional group.

[0057] The organyl group is hydrocarbyl, substituted hydrocarbyl, heterocyclyl, or substituted heterocyclyl. In certain embodiments, each of R2, R3, R4, and Rs is independently H, alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl, alkynyl, heterocyclyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy, nitrile, or halo. In other embodiments, each of R2, R3, R4, and Rs is independently H, alkyl, cycloalkyl, aryl, cycloalkenyl, alkynyl, heterocyclyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy, nitrile, or halo. In further embodiments, each of R2, R3, R4, and Rs is independently H, alkyl, or aryl.

[0058] In some embodiments, at least one of R2, R3, R4, and Rs is an organyl group. In other embodiments, at least two of R2, R3, R4, and Rs are an organyl group. For instance, R3 and Rs may be organyl groups. In furtherembodiments, at least one of R2, R3, R4, and Rs is H. In other embodiments, at least two of R2, R3, R4, and Rs are H. For instance, R2 and R4 may be H.

[0059] In certain embodiments, at least one of R2, R3, R4, and Rs is H. In other embodiments, each of R2, R3, R4, and Rs is H. In further embodiments, R2 is hydrocarbyl, and each of R3, R4, and Rs is H. In still further embodiments, the hydrocarbyl is alkyl, cycloalkyl, or aryl. In still further embodiments, none of R2, R3, R4, and Rs is or comprises alkenyl, cycloalkenyl, or alkynyl.

[0060] In certain embodiments, R3 is aryl and each of R2, R4, and Rs is H. In further embodiments, R3 is phenyl, and each of R2, R4, and Rs is H. In certain other embodiments, R3 is aryl, Rs is alkyl, and each of R2 and R4 is H. In further embodiments, R3 is phenyl, Rs is alkyl, and each of R2 and R4 is H.

[0061] In certain embodiments, at least one of R2, R3, R4, and Rs is a functional group containing halo, O, N, S, P or a combination thereof. Some nonlimiting examples of suitable functional groups include hydroxy, alkoxy, aryloxy, amino, nitro, thiol, thioether, imine, cyano, amido, phosphonato ( — P(=O)(O-alkyl)2, — P(=O)(O-aryl)2, or — P(=O)(O-alkyl))O-aryl), phosphinato ( — P(=O)(O- alkyl)alkyl, — P(=O)(O-aryl)alkyl, — P(=O)(O-alkyl)aryl, or — P(=O)(O-aryl)aryl), carboxyl, thiocarbonyl, sulfonyl ( — S(=O)2alkyl, or — S(=O)2aryl), sulfonamide ( — SO2NH2, — SO2NH(alkyl), — SO2NH(aryl), — SO2N(alkyl)2, — SO2N(aryl)2, or — SO2N(aryl)(alkyl)), ketone, aldehyde, ester, oxo, amino (primary, secondary or tertiary), — CO2CH3, — CONH2, — OCH2CONH2, — NH2, — OCHF2, — OCF3, — NH(alkyl), — N(alkyl)2, — NH(aryl), — N(alkyl)(aryl), — N(aryl)2, — CHO, — CO(alkyl), — CO(aryl), — CC>2(alkyl), or — CO2(aryl). In some embodiments, the functional group is or comprises alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy, nitrile, or halo. In other embodiments, none of R2, R3, R4, and Rs is or comprises a functional group. In other embodiments, none of R2, R3, R4, and Rs is or comprises alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, acyloxy, nitrile, or halo.

[0062] In some embodiments, the vinyl compound is a substituted or unsubstituted olefin such as ethylene or styrene, vinyl halide, vinyl ether, acrylonitrile, acrylic ester, methacrylic ester, acrylamide, methacrylamide, or a combination thereof. In other embodiments, the vinyl compound is ethylene, an a- olefin, or a combination thereof. Some non-limiting examples of suitable a-olefinsinclude styrene, propylene, 1 -butene, 1 -hexene, 1 -octene, 4-methyl-1 -pentene, norbornene, 1 -decene, 1 ,5-hexadiene and combinations thereof.

[0063] In some embodiments, the vinyl compound modifying agent is an aromatic vinyl compound modifying agent. For instance, the aromatic vinyl compound modifying agent may be a styrene or a derivative thereof. In particular, the aromatic vinyl compound modifying agent may be styrene, a-methylstyrene, 2- methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4- diisopropylstyrene, 4-propylstyrene, 3-ethylstyrene, 4-ethylstyrene, 4- cyclohexylstyrene, 4-(p-methylphenyl)styrene, 5-tert-butyl-2-methylstyrene, tertbutoxystyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, N,N- dimethylaminoethylstyrene, chlorostyrene (e.g., mono-, di-, tri-, tetra- and pentachlorostyrene), bromostyrene (e.g., mono-, di-, tri-, tetra- and pentabromostyrene), chloromethyl styrene, methoxy-styrene, acetoxy-styrene, 1 -vinyl-5- hexylnaphthalene, 1-vinylnaphthalene, divinylnaphthalene, divinylbenzene, trivinylbenzene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethylether, vinylpyridine, vinylxylene, diphenylethylene, diphenylethylene including a tertiary amine, styrene including a primary, secondary, or tertiary amine, and a combination of two or more thereof. In one particular embodiment, the vinyl compound modifying agent may be a styrene, such as a-methylstyrene. Additional examples include the functionalized vinyl aryls such as those disclosed by U.S. Pat. No. 7,041 ,761 which is incorporated herein by reference.

[0064] In one embodiment, the aromatic vinyl compound modifying agent may correspond to the following general structural formula (VI) :whereinRe is hydrogen or a hydrocarbyl group, such as an alkyl group and in particular a methyl group; o is 0 or an integer ranging from 1 to 5; andY is a halogen (e.g., chlorine or bromine), a saturated or unsaturated alkyl, or an alkoxyl having from 1 to 4 carbon atoms.

[0065] As indicated above, Re is hydrogen or a hydrocarbyl group. In one embodiment, Re is hydrogen or a hydrocarbyl group. For instance, the hydrocarbyl group may be one as defined above with respect to Ri. In particular, the hydrocarbyl group may be an alkyl group, in particular a lower alkyl group. For instance, the alkyl group may have 1 or more, such as 2 or more, such as 3 or more, such as 4 of more carbon atoms. Such alkyl group may have 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms. In one particular embodiment, Re may be a hydrocarbyl group, such as methyl.

[0066] In addition, in one embodiment, o is 0. In another embodiment, o is an integer of from 1 to 5, such as 1 to 3, such as 1 to 2, such as 1 .

[0067] As indicated above, Y is a halogen (e.g., chlorine or bromine), a saturated or unsaturated alkyl, or an alkoxyl having from 1 to 4 carbon atoms. In one embodiment, Y is a halogen, such as chlorine or bromine. In another embodiment, Y is a saturated or unsaturated alkyl. In a further embodiment, Y is an alkoxyl having from 1 to 4 carbon atoms.

[0068] In this regard, in one embodiment, the modified novolak resin may have the following structural formula (VII):whereinRi is as defined above;Re is as defined above; n is as defined above;Y is as defined above; and o is as defined above.

[0069] Even further, in one embodiment when o is 0, the modified novolak resin may have the following structural formula (Vila):whereinRi is as defined above; Re is as defined above; and n is as defined above.

[0070] Vinyl compound modifying agents may also include (meth)acrylonitrile, vinyl esters, vinyl halides, vinylidene halides, acrylic acid and esters and derivatives thereof, and mixtures thereof. Examples of vinyl esters include, but are not limited to, vinyl acetate, vinyl chloroacetate, and vinyl propionate. Examples of vinyl halides may include, but are not limited to, vinyl chloride and vinyl bromide. Examples of vinylidene halides may include, but are not limited to, vinylidene chloride. Examples of (meth)acrylic acid and esters and derivatives thereof may include, but are not limited to, acrylic acid, methacrylic acid, and esters (also referred to as (meth)acrylic esters) and derivatives thereof. For instance, they may include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate (e.g., isopropyl acrylate), butyl acrylate (e.g., isobutyl acrylate, t-butyl acrylate), hexyl acrylate, octyl acrylate, lauryl acrylate, cyanoethyl acrylate, 2-ethylhexyl-acrylate, chloroethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate (e.g., isopropyl methacrylate), butyl methacrylate (e.g., isobutyl methacrylate, t-butyl methacrylate), hexyl methacrylate, 2-ethylhexyl-methacrylate, lauryl methacrylate, and mixtures thereof.

[0071] The vinyl compound modifying agents containing carboxyl groups can be selected from derivatives of acrylic and methacrylic acids such as esters, anhydrides and chlorides. Examples of vinyl compound modifying agents include, but are not limited to: maleic anhydride, maleic acid chloride, maleic acid esters deriving from alcohols having from 1 to 8 carbon atoms, acrylic acid, acrylic acid chloride, acrylic acid anhydrides, acrylic acid esters deriving from alcohols having from 1 to 8 carbon atoms, methacrylic acid, methacrylic acid chloride, methacrylicacid anhydrides, methacrylic acid esters deriving from alcohols having from 1 to 8 carbon atoms .

[0072] The vinyl compound modifying agent may be a halogen group containing vinyl compound (e.g., 2-chloroethyl vinyl ether, vinyl chloroacetate, vinyl a-chloropropionate, allyl chloroacetate, chloroethyl acrylate, chloromethyl styrene, etc.). The vinyl compound modifying agent may be an epoxy group-containing compound (e.g., vinyl glycidyl ether, allyl glycidyl ether, glycidyl (meth)acrylate, etc ). The vinyl compound modifying agent may be a hydroxyl group-containing vinyl compound (e.g., hydroxyalkyl (meth)acrylate (such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate), hydroxyalkoxy acrylate, N- methylolacrylamide, etc.). The vinyl compound modifying agent may be an amide group-containing vinyl compound (e.g., acrylamide, methacrylamide, N- methylol(meth)acrylamide, methylolacrylamide, etc.).

[0073] Examples of vinyl compound modifying agents include, but are not limited to: ring-containing unsaturated compounds such as styrene and o-,m-,p- substitution products thereof such as N,N-dimethylaminostyrene, aminostyrene, hydroxystyrene, t-butylstyrene, vinyltoluene, carboxystyrene and the like, alphamethylstyrene, phenyl (meth)acrylates, nitro-containing hydrocarbyl (meth)acrylates such as N,N-dimethylaminoethyl methacrylate, N-t-butylaminoethyl methacrylate; 2-(dimethylamino)ethyl methacrylate, methylchloride quaternized salt, and the like; olefins or diene compounds such as ethylene, propylene, butylene, isobutene, isoprene, chloropropene, fluorine containing olefins, vinyl chloride, and the like; carboxyl group-containing unsaturated monomers such as acrylic acid, methacrylic acid, cratonic acid, itaconic acid, maleic acid, fumaric acid, and the like (preferably methacrylic acid), C2-C8 hydroxyl hydrocarbyl esters of (meth)acrylic acid (preferably methacrylic acid) such as 2-hydroxylethyl (meth)acrylate, 2-hydroxylpropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and the like, monoesters between a polyether polyol (e.g., polyethylene glycol, polypropylene glycol or polybutylene glycol) and an unsaturated carboxylic acid (preferably methacrylic acid); monoethers between a polyether polyol (e.g., polyethylene glycol, polypropylene glycol or polybutylene glycol) and a hydroxyl group-containing unsaturated monomers (e.g., 2-hydroxyl methacrylate); adducts between an unsaturated carboxylic acid and a monoepoxy compound; adducts between glycidyl (meth)acrylates (preferably methacrylate)and a monobasic acid (e.g., acetic acid, propionic acid, p-t-butylbenzoic acid or a fatty acid); monoesters or diesters between an acid anhydride group-containing unsaturated compound (e.g., maleic anhydride or iraconic anhydride) and a glycol (e.g. ethylene glycol, 1 ,6-hexanediol or neopentyl glycol); chlorine-, bromine-, fluorine-, and hydroxyl group containing monomers such as 3-chloro-2- hydroxylpropyl (meth)acrylate (preferably methacrylate) and the like; C1-C24 hydrocarbyl esters or cyclohydrocarbyl esters of (meth)acrylic acid (preferably methacrylic acid), such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-, sec-, or t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate and the like, C2- C18 alkoxyhydrocarbyl esters of (meth)acrylic acid (preferably methacrylic acid), such as methoxybutyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, ethoxybutyl methacrylate and the like; polymerizable amides such as (meth)acrylamide, N-methyl(meth)acrylamide, 2-acryloamido-2-methyl-1- propanesulfonic acid, and the like; nitrogen-containing monomers such as 2-, 4- vinyl pyridines, 1-vinyl-2-pyrrolidone, (meth)acrylonitrile, and the like; glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylates and the like, vinyl ethers, vinyl acetate, and cyclic monomers such as methyl 1 ,1- bicyclobutanecarboxylate. These monomers can be used singly or as a mixture.

[0074] In addition to the above, as indicated herein, a dimer of the vinyl compound modifying agent may be used to modify the hydrocarbylphenol. Similarly, the residue of the hydrocarbylphenol may be a dimer of a vinyl compound modifying agent as defined herein. Accordingly, the dimer may react with the hydrocarbylphenol to form the vinyl compound modified hydrocarbylphenol. Alternatively, the vinyl compound modifying agent may react with the hydrocarbylphenol and then a subsequent reaction with the vinyl compound modifying agent may be conducted to form the dimer to form the vinyl compound modified hydrocarbylphenol.

[0075] The vinyl compound modifying agent may be provided for the synthesis in an amount of about 0.01 wt.% or more, such as about 0.05 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.5 wt.% or more, such as about 0.8 wt.% or more, such as about 1 wt.% or more, such as about 1.2 wt.% or more, such as about 1 .5 wt.% or more, such asabout 2 wt.% or more, such as about 2.5 wt.% or more, such as about 3 wt.% or more, such as about 3.5 wt.% or more, such as about 4 wt.% or more, such as about 5 wt.% or more, such as about 6 wt.% or more, such as about 7 wt.% or more, such as about 8 wt.% or more, such as about 9 wt.% or more, such as about 10 wt.% or more, such as about 12 wt.% or more, such as about 15 wt.% or more based on the weight of the hydrocarbylphenol. The vinyl compound modifying agent may be provided in an amount of about 25 wt.% or less, such as about 22 wt.% or less, such as about 20 wt.% or less, such as about 18 wt.% or less, such as about 16 wt.% or less, such as about 14 wt.% or less, such as about 12 wt.% or less, such as about 10 wt.% or less, such as about 8 wt.% or less, such as about 6 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less based on the weight of the hydrocarbylphenol.

[0076] The molar ratio of the vinyl compound modifying agent to the hydrocarbylphenol may be 0.001 or more, such as about 0.005 or more, such as about 0.01 or more, such as about 0.02 or more, such as about 0.03 or more, such as about 0.05 or more, such as about 0.08 or more, such as about 0.1 or more, such as about 0.12 or more, such as about 0.15 or more, such as about 0.2 or more, such as about 0.25 or more, such as about 0.3 or more, such as about 0.4 or more, such as about 0.5 or more, such as about 0.7 or more, such as about 0.8 or more, such as about 0.9 or more, such as about 1 or more. The molar ratio may be 3 or less, such as about 2 or less, such as about 1 .5 or less, such as about 1 or less, such as about 0.9 or less, such as about 0.8 or less, such as about 0.6 or less, such as about 0.4 or less, such as about 0.3 or less, such as about 0.2 or less, such as about 0.15 or less.

[0077] As indicated above, the hydrocarbylphenol may be reacted with an aldehyde and / or ketone as generally known in the art. In one embodiment, the hydrocarbylphenol may be reacted with an aldehyde. In another embodiment, the hydrocarbylphenol may be reacted with a ketone.

[0078] In general, the aldehyde may include, but is not limited to, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanecarbaldehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, a-phenylpropylaldehyde, - phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p- methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p- chlorobenzaldehyde, cinnamaldehyde, or a mixture thereof. The aldehydes may be used alone or in combination. In one embodiment, the aldehyde may be formaldehyde. In particular, the formaldehyde may be provided as an aqueous formulation.

[0079] The ketone may include, but is not limited to, acetone, methylethylketone, diethylketone, diphenylketone, or a mixture thereof. The ketones may be used alone or in combination.

[0080] The aldehyde and / or ketone, in particular the aldehyde, may be provided for the synthesis in a particular amount. For instance, the molar ratio of the aldehyde and / or ketone, in particular the aldehyde, to the hydrocarbylphenol may be about 0.1 or more, such as about 0.2 or more, such as about 0.3 or more, such as about 0.4 or more, such as about 0.5 or more, such as about 0.6 or more, such as about 0.65 or more, such as about 0.7 or more, such as about 0.75 or more, such as about 0.8 or more, such as about 0.85 or more, such as about 0.9 or more, such as about 0.95 or more, such as about 1 or more. The molar ratio may be about 5 or less, such as about 4 or less, such as about 3 or less, such as about 2 or less, such as about 1 .8 or less, such as about 1 .6 or less, such as about 1 .4 or less, such as about 1.2 or less, such as about 1.1 or less, such as about 1 .05 or less, such as about 1 or less, such as about 0.98 or less, such as about 0.95 or less, such as about 0.93 or less, such as about 0.9 or less. In one embodiment, the aforementioned molar ratio may be based on the aldehyde and / or ketone, in particular the aldehyde, and the combination of the hydrocarbylphenol and the vinyl compound modified hydrocarbylphenol as disclosed herein.

[0081] The weight ratio of the aldehyde and / or ketone, in particular the aldehyde, to the hydrocarbylphenol may be about 0.001 or more, such as about 0.005 or more, such as about 0.01 or more, such as about 0.02 or more, such as about 0.03 or more, such as about 0.05 or more, such as about 0.08 or more, such as about 0.1 or more, such as about 0.12 or more, such as about 0.15 or more, such as about 0.2 or more, such as about 0.3 or more, such as about 0.4 or more, such as about 0.5 or more, such as about 0.7 or more, such as about 0.8 or more, such as about 0.9 or more, such as about 1 or more. The weight ratio may beabout 3 or less, such as about 2 or less, such as about 1 .5 or less, such as about 1 or less, such as about 0.9 or less, such as about 0.8 or less, such as about 0.6 or less, such as about 0.4 or less, such as about 0.3 or less, such as about 0.2 or less, such as about 0.15 or less. In one embodiment, the aforementioned weight ratio may be based on the aldehyde and / or ketone, in particular the aldehyde, and the combination of the hydrocarbylphenol and the vinyl compound modified hydrocarbylphenol as disclosed herein.

[0082] Generally, the polymerization of hydrocarbylphenols with an aldehyde and / or ketone to prepare novolak resins is well known in the art. The highly exothermic condensation reaction, so called “novolak condensation,” is carried out by a method including reacting a hydrocarbylphenol with an aldehyde, such as formaldehyde, or ketone in the presence of a catalyst.

[0083] The method may be carried out in any appropriate reaction vessel. The hydrocarbylphenol and the vinyl modified hydrocarbylphenol may be brought to a desired reaction temperature and the aldehyde and / or ketone may be provided over a period of time. It is also possible to initially introduce only a part of the hydrocarbylphenol and to add the rest along with the aldehyde and / or ketone at a later time. After condensation is complete, the reaction may be neutralized by a base and the water may be removed, such as by distillation. Distillation may also be utilized to further purify the novolak resin composition to remove other relatively low molecular weight components (e.g., low boilers, para-tert- butylphenol, para-tert-octylphenol, etc.).

[0084] The reaction may be conducted at a temperature of 50°C or more, such as about 70°C or more, such as about 90°C or more, such as about 110°C or more, such as about 130°C or more, such as about 150°C or more, such as about 170°C or more, such as about 190°C or more. The reaction may be conducted at a temperature of 300°C or less, such as about 270°C or less, such as about 240°C or less, such as about 220°C or less, such as about 210°C or less, such as about 200°C or less, such as about 190°C or less, such as about 180°C or less, such as about 170°C or less, such as about 160°C or less, such as about 150°C or less, such as about 140°C or less, such as about 130°C or less, such as about 120°C or less.

[0085] The catalyst is not necessarily limited by the present invention. In this regard, the catalyst may be a Friedel Crafts catalyst and / or an acid catalyst. Inone particular embodiment, the catalyst may be an acid catalyst. For instance, the acid catalyst may include an inorganic acid such as hydrochloric, sulfuric, phosphoric, or phosphorous. The acid catalyst may also include the alkyl and arylsulfonic acids such as benzenesulfonic acid, benzenedisulfonic acid, or methanesulfonic acid. One preferred catalyst may include an arylsulfonic acid catalyst. For instance, the acid catalyst may include toluenesulfonic acid, xylenesulfonic acid, or dodecylbenzene sulfonic acid. In one particular embodiment, the catalyst may include an acid catalyst which may include dodecylbenzene sulfonic acid.

[0086] The catalyst may be provided in an amount necessary for the reaction. In this regard, the catalyst may be present in an amount of about 0.01 wt.% or more, such as about 0.02 wt.% or more, such as about 0.05 wt.% or more, such as about 0.1 wt.% or more, such as about 0.15 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.5 wt.% or more, such as about 0.7 wt.% or more, such as about 1 wt.% or more, such as about 1 .2 wt.% or more, such as about 1 .5 wt.% or more based on the weight of the hydrocarbylphenol. The catalyst may be present in an amount of about 10 wt.% or less, such as about 8 wt.% or less, such as about 6 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 .8 wt.% or less, such as about 1 .6 wt.% or less, such as about 1 .4 wt.% or less, such as about 1.2 wt.% or less, such as about 1.0 wt.% or less, such as about 0.9 wt.% or less, such as about 0.8 wt.% or less, such as about 0.7 wt.% or less, such as about 0.6 wt.% or less, such as about 0.5 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less based on the weight of the hydrocarbylphenol.

[0087] The molar ratio of the catalyst to the hydrocarbylphenol may be 0.0001 or more, such as about 0.0005 or more, such as about 0.001 or more, such as about 0.0015 or more, such as about 0.002 or more, such as about 0.003 or more, such as about 0.005 or more. The molar ratio may be 0.1 or less, such as about 0.05 or less, such as about 0.03 or less, such as about 0.01 or less, such as about 0.008 or less, such as about 0.006 or less, such as about 0.004 or less, such as about 0.003 or less, such as about 0.002 or less.

[0088] In one embodiment, the method may further comprise a step of neutralizing the catalyst. In this regard, the method may include a step ofproviding a base, such as upon completion of the synthesis. The base is not necessarily limited by the present invention and any base that may neutralize the catalyst, in particular an acid catalyst, may be utilized. The base may include sodium hydroxide as well as amines, such as TEA (triethylamine) and / or TEAOH (triethanolamine). In one particular embodiment, the base may include triethylamine. In another embodiment, the base may include triethanolamine.

[0089] The base may be provided in an amount necessary for the neutralization. In this regard, the base may be provided in an amount of about 0.01 wt.% or more, such as about 0.02 wt.% or more, such as about 0.05 wt.% or more, such as about 0.08 wt.% or more, such as about 0.1 wt.% or more, such as about 0.12 wt.% or more, such as about 0.14 wt.% or more, such as about 0.16 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.5 wt.% or more, such as about 0.7 wt.% or more, such as about 1 wt.% or more, such as about 1 .2 wt.% or more, such as about 1 .5 wt.% or more based on the weight of the hydrocarbylphenol. The base may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1.8 wt.% or less, such as about 1.6 wt.% or less, such as about 1 .4 wt.% or less, such as about 1 .2 wt.% or less, such as about 1 .0 wt.% or less, such as about 0.9 wt.% or less, such as about 0.8 wt.% or less, such as about 0.7 wt.% or less, such as about 0.6 wt.% or less, such as about 0.5 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less based on the weight of the hydrocarbylphenol.

[0090] The molar ratio of the base to the catalyst may be 0.1 or more, such as about 0.2 or more, such as about 0.3 or more, such as about 0.4 or more, such as about 0.5 or more, such as about 0.6 or more, such as about 0.7 or more, such as about 0.8 or more, such as about 0.9 or more, such as about 1 or more, such as about 1.2 or more, such as about 1 .4 or more, such as about 1 .6 or more, such as about 1.8 or more, such as about 2 or more. The molar ratio may be 10 or less, such as about 8 or less, such as about 6 or less, such as about 4 or less, such as about 3 or less, such as about 2.8 or less, such as about 2.6 or less, such as about 2.4 or less, such as about 2.2 or less, such as about 2.1 or less, such as about 2 or less, such as about 1 .9 or less, such as about 1 .8 or less, such as about 1 .7 or less, such as about 1 .6 or less, such as about 1 .5 or less, such as about 1 .4 orless, such as about 1 .3 or less, such as about 1 .2 or less, such as about 1 .1 or less, such as about 1 or less.

[0091] The molar ratio of the base to the hydrocarbylphenol may be 0.0001 or more, such as about 0.0005 or more, such as about 0.001 or more, such as about 0.0015 or more, such as about 0.002 or more, such as about 0.0025 or more, such as about 0.003 or more, such as about 0.005 or more. The molar ratio may be 0.1 or less, such as about 0.05 or less, such as about 0.03 or less, such as about 0.01 or less, such as about 0.008 or less, such as about 0.006 or less, such as about 0.004 or less, such as about 0.003 or less, such as about 0.002 or less.

[0092] The method may also include a step of removing any water generated during the reaction and / or introduced during the reaction. As an example, water may be present within the aqueous formaldehyde utilized in reacting with the hydrocarbylphenol. The removal of water may be done using any technique generally known in the art. For instance, the water may be removed via distillation. As indicated above, distillation may also be utilized to further purify the novolak resin composition to remove other relatively low molecular weight components (e.g., low boilers, para-tert-butylphenol, para-tert-octylphenol, etc.).

[0093] As indicated above, the novolak resin composition may include a low concentration of other components, such as SVHCs and / or remainder hydrocarbylphenol. In this regard, the modified novolak resin(s) may be present in an amount of 80 wt.% or more, such as about 85 wt.% or more, such as about 88 wt.% or more, such as about 90 wt.% or more, such as about 92 wt.% or more, such as about 94 wt.% or more, such as about 95 wt.% or more, such as about 96 wt.% or more, such as about 97 wt.% or more, such as about 98 wt.% or more, such as about 99 wt.% or more, such as about 99.5 wt.% or more based on the weight of the novolak resin composition.

[0094] The novolak resin composition may include a first modified novolak resin of structural formula (I) and a second modified novolak resin of structural formula (I), wherein such modified novolak resins satisfy the definitions herein. In one embodiment, the novolak resin composition may also include a third modified novolak resin of structural formula (I), wherein such modified novolak resin satisfies the definitions herein. As examples, the first modified novolak resin of structural formula (I) may include a novolak resin wherein both ends are capped by the vinyl compound modifying agent and / or a dimer thereof(e.g., wherein both of zand x are at least 1 in formula (I)). Meanwhile, the second compound of structural formula (I) may include a novolak resin wherein only one end is capped by the vinyl compound modifying agent or a dimer thereof(e.g., wherein one of z and x is 0 while the other of z and x is 1 in formula (I)).

[0095] When the novolak resin composition includes both a first modified novolak resin of structural formula (I) and a second modified novolak resin of structural formula (I), they may be included in certain amounts. For instance, the first modified novolak resin of structural formula (I) may be present in an amount of about 0.01 wt.% or more, such as about 0.1 wt.% or more, such as about 0.5 wt.% or more, such as about 1 wt.% or more, such as about 2 wt.% or more, such as about 3 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more, such as about 40 wt.% or more, such as about 50 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or more, such as about 80 wt.% or more, such as about 90 wt.% or more, such as about 95 wt.% or more, such as about 97 wt.% or more, such as about 98 wt.% or more, such as about 99 wt.% or more. The first modified novolak resin of structural formula (I) may be present in an amount of about 100 wt.% or less, such as about 99.5 wt.% or less, such as about 99 wt.% or less, such as about 98 wt.% or less, such as about 97 wt.% or less, such as about 95 wt.% or less, such as about 90 wt.% or less, such as about 85 wt.% or less, such as about 80 wt.% or less, such as about 75 wt.% or less, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 50 wt.% or less, such as about 40 wt.% or less, such as about 30 wt.% or less, such as about 20 wt.% or less, such as about 10 wt.% or less. The aforementioned weight percentage may be based on the weight of the novolak resin composition in one embodiment. In another embodiment, the aforementioned weight percentage may be based on the total weight of the modified novolak resins of structural formula (I) present in the novolak resin composition.

[0096] Similarly, the second modified novolak resin of structural formula (I) may be present in an amount of about 0.01 wt.% or more, such as about 0.1 wt.% or more, such as about 0.5 wt.% or more, such as about 1 wt.% or more, such as about 2 wt.% or more, such as about 3 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such asabout 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more, such as about 40 wt.% or more, such as about 50 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or more, such as about 80 wt.% or more, such as about 90 wt.% or more, such as about 95 wt.% or more, such as about 97 wt.% or more, such as about 98 wt.% or more, such as about 99 wt.% or more. The second modified novolak resin of structural formula (I) may be present in an amount of about 100 wt.% or less, such as about 99.5 wt.% or less, such as about 99 wt.% or less, such as about 98 wt.% or less, such as about 97 wt.% or less, such as about 95 wt.% or less, such as about 90 wt.% or less, such as about 85 wt.% or less, such as about 80 wt.% or less, such as about 75 wt.% or less, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 50 wt.% or less, such as about 40 wt.% or less, such as about 30 wt.% or less, such as about 20 wt.% or less, such as about 10 wt.% or less. The aforementioned weight percentage may be based on the weight of the novolak resin composition in one embodiment. In another embodiment, the aforementioned weight percentage may be based on the total weight of the modified novolak resins of structural formula (I) present in the novolak resin composition.

[0097] As also indicated, the hydrocarbylphenols including two hydrocarbyl groups may also be utilized. In this regard, such hydrocarbylphenol may form one or both end caps. For instance, in the instance it forms one end cap, the novolak resin composition may include a second novolak resin having the following structural formula (VIII):whereinRi is as defined above;V is as defined above;Rz is as defined above; n is as defined above; and z is as defined above.

[0098] In the instance it forms both end caps, the novolak resin composition may include a third novolak resin having the following structural formula (IX):whereinRi is as defined above;R7 is as defined above; and n is as defined above.

[0099] As indicated above, R7 is an optionally substituted hydrocarbyl group. In one embodiment, such hydrocarbyl group may be an alkyl group, in particular a lower alkyl group. For instance, the alkyl group may have 1 or more, such as 2 or more, such as 3 or more, such as 4 of more carbon atoms. Such alkyl group may have 8 or less, such as 6 or less, such as 5 or less, such as 4 or less, such as 3 or less, such as 2 or less carbon atoms.

[0100] The modified novolak resin of structural formula (VIII) may be present in the novolak resin composition in a relatively low amount. For instance, it may be present in an amount of about 15 wt.% or less, such as about 12 wt.% or less, such as about 10 wt.% or less, such as about 8 wt.% or less, such as about 6 wt.% or less, such as about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.8 wt.% or less, such as about 0.6 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less based on the weight of the novolak resin composition. It may be present in an amount of 0 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more, such as about 0.8 wt.% or more, such as about 1 wt.% or more, such as about 1 .5 wt.% or more, such as about 2 wt.% or more based on the weight of the novolak resin composition.

[0101] The modified novolak resin of structural formula (IX) may also be present in the novolak resin composition in a relatively low amount. For instance,it may be present in an amount of about 15 wt.% or less, such as about 12 wt.% or less, such as about 10 wt.% or less, such as about 8 wt.% or less, such as about 6 wt.% or less, such as about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.8 wt.% or less, such as about 0.6 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less based on the weight of the novolak resin composition. It may be present in an amount of 0 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more, such as about 0.8 wt.% or more, such as about 1 wt.% or more, such as about 1 .5 wt.% or more, such as about 2 wt.% or more based on the weight of the novolak resin composition.

[0102] The novolak resin composition may, in one embodiment, also include a novolak resin that is not modified (i.e. , unmodified novolak resin). For instance, this may include a novolak resin that does not include an end-cap formed from a vinyl compound modifying agent or a dimer thereof as defined herein but instead the hydrocarbylphenol utilized in forming the novolak resin forms the ends. Such novolak resin may be present in an amount of 25 wt.% or less, such as about 20 wt.% or less, such as about 18 wt.% or less, such as about 15 wt.% or less, such as about 13 wt.% or less, such as about 10 wt.% or less, such as about 9 wt.% or less, such as about 8 wt.% or less, such as about 6 wt.% or less, such as about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.8 wt.% or less, such as about 0.6 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less based on the weight of the novolak resin composition. Such novolak resin may be present in an amount of 0 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more, such as about 0.8 wt.% or more, such as about 1 wt.% or more, such as about 1.5 wt.% or more, such as about 2 wt.% or more, such as about 3 wt.% or more, such as about 4 wt.% or more, such as about 5 wt.% or more, such as about 6 wt.% or more, such as about 7 wt.% or more, such as about 8 wt.% or more, such as about 9 wt.% or more, such as about 10 wt.% or more based on the weight of the novolak resin composition.

[0103] The novolak resin composition may, in one embodiment, also include a novolak resin that is formed from phenol (i.e., without a hydrocarbyl substituent). Such novolak resin may be present in an amount of 10 wt.% or less, such as about 9 wt.% or less, such as about 8 wt.% or less, such as about 6 wt.% or less, such as about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.8 wt.% or less, such as about 0.6 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less based on the weight of the novolak resin composition. Such novolak resin may be present in an amount of 0 wt.% or more, such as about 0.001 wt.% or more, such as about 0.01 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more, such as about 0.8 wt.% or more, such as about 1 wt.% or more, such as about 1.5 wt.% or more, such as about 2 wt.% or more, such as about 3 wt.% or more based on the weight of the novolak resin composition.

[0104] In addition, because the phenol utilized in forming the aforementioned novolak resin may not have any hydrocarbyl substituents, the resulting novolak resin may be linear (i.e., only ortho-ortho reactions), non-linear (i.e., including at least one ortho-para reaction), or a mixture thereof. For instance, in one embodiment, the novolak resin formed from phenol may be linear. In another embodiment, the novolak resin formed from phenol may be non-linear. In a further embodiment, the novolak resin formed from phenol may include a mixture of linear and non-linear resins.

[0105] The novolak resin composition may also include other novolak resins based on a combination of a hydrocarbylphenol and phenol and optionally a vinyl compound modified hydrocarbylphenol and / or a vinyl compound modified phenol. For instance, such novolak resin may have the following structural formula (X):whereinRi is as defined above;V is as defined above;W is as defined above; n is 1 or more; j is from 0 to 1 ; k is from 0 to 1 ; g is from 0 to 1 ; and h is from 0 to 1 , wherein at least one of g and h is 0.

[0106] In the structure of formula (X), when either g or h is 0, such component may be formed from phenol. Furthermore, such phenol may be optionally modified with the vinyl compound modifying agent and / or a dimer thereof as defined herein. In particular, the modification may occur in a similar manner as the modification to the hydrocarbylphenol with the exception that the phenol does not include a hydrocarbyl group. However, when j and g are 0, such component may be formed from phenol such that the resin is end-capped with phenol and not modified. Similarly, when k and h are 0, such component may be formed from phenol such that the resin is end-capped with phenol and not modified.

[0107] As also illustrated in the structure above, the bond between the hydrocarbylphenol and the end-caps may be ortho-ortho or ortho-para depending on the existence of Ri within the end-cap. For instance, if g is 1 or h is 1 , such reaction may be ortho-ortho between the hydrocarylphenol and the respective endcap, whether phenol or vinyl compound modified phenol. However, if g is 0 or h is 0, the reaction may be ortho-para between the hydrocarylphenol and the respective end-cap, whether phenol or vinyl compound modified phenol.Accordingly, the novolak resin of formula (X) may be linear (i.e., only ortho-ortho reactions), non-linear (i.e., including at least one ortho-para reaction), or a mixture thereof. For instance, in one embodiment, such novolak resin may be linear. In another embodiment, such novolak resin may be non-linear. In a further embodiment, such novolak resin may include a mixture of linear and non-linear resins.

[0108] Such novolak resin of formula (X) may be present in the novolak resin composition in a particular amount. For instance, such novolak resin may be present in an amount of 10 wt.% or less, such as about 9 wt.% or less, such asabout 8 wt.% or less, such as about 6 wt.% or less, such as about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.8 wt.% or less, such as about 0.6 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less based on the weight of the novolak resin composition. Such novolak resin may be present in an amount of 0 wt.% or more, such as about 0.001 wt.% or more, such as about 0.01 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more, such as about 0.8 wt.% or more, such as about 1 wt.% or more, such as about 1 .5 wt.% or more, such as about 2 wt.% or more, such as about 3 wt.% or more based on the weight of the novolak resin composition.

[0109] The novolak resin composition may also contain a relatively low concentration of phenol. For instance, phenol may be present in an amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3.5 wt.% or less, such as about 3 wt.% or less, such as about 2.5 wt.% or less, such as about 2 wt.% or less, such as about 1.8 wt.% or less, such as about 1.6 wt.% or less, such as about 1.4 wt.% or less, such as about 1 .2 wt.% or less, such as about 1 wt.% or less, such as about 0.9 wt.% or less, such as about 0.8 wt.% or less, such as about 0.7 wt.% or less, such as about 0.6 wt.% or less, such as about 0.5 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less. Phenol may be present in an amount of 0 wt.% or more, such as about 0.001 wt.% or more, such as about 0.005 wt.% or more, such as about 0.01 wt.% or more, such as about 0.03 wt.% or more, such as about 0.05 wt.% or more, such as about 0.08 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more, such as about 1 wt.% or more. In one embodiment, the aforementioned weight percentages may be based on the weight of the novolak resin composition. In another embodiment, the aforementioned weight percentages may be based on the weight of the one or more modified novolak resins.

[0110] The novolak resin composition may also contain a relatively low concentration of free alkanes (e.g., butane, octane, dodecane, etc.). For instance, free alkanes may be present in an amount of about 5 wt.% or less, such as about 4wt.% or less, such as about 3.5 wt.% or less, such as about 3 wt.% or less, such as about 2.5 wt.% or less, such as about 2 wt.% or less, such as about 1 .8 wt.% or less, such as about 1 .6 wt.% or less, such as about 1 .4 wt.% or less, such as about 1 .2 wt.% or less, such as about 1 wt.% or less, such as about 0.9 wt.% or less, such as about 0.8 wt.% or less, such as about 0.7 wt.% or less, such as about 0.6 wt.% or less, such as about 0.5 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less. Free alkanes may be present in an amount of 0 wt.% or more, such as about 0.001 wt.% or more, such as about 0.005 wt.% or more, such as about 0.01 wt.% or more, such as about 0.03 wt.% or more, such as about 0.05 wt.% or more, such as about 0.08 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more, such as about 1 wt.% or more. In one embodiment, the aforementioned weight percentages may be based on the weight of the novolak resin composition. In another embodiment, the aforementioned weight percentages may be based on the weight of the one or more modified novolak resins.

[0111] As indicated herein, in one embodiment, the vinyl compound modifying agent may also form dimers and / or trimers. Such compounds may be referred to as a vinyl compound modifying agent dimer and vinyl compound modifying agent trimer, respectively. In this regard, dimers and / or trimers may be present in the novolak resin composition in an amount of about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.8 wt.% or less, such as about 0.6 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less based on the weight of the novolak resin composition. Such dimers and / or trimers may be present in an amount of 0 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.3 wt.% or more, such as about 0.4 wt.% or more, such as about 0.5 wt.% or more, such as about 0.8 wt.% or more, such as about 1 wt.% or more, such as about 1.5 wt.% or more, such as about 2 wt.% or more based on the weight of the novolak resin composition.

[0112] The modified novolak resin may have a particular softening point of about 50°C or more, such as about 60°C or more, such as about 70°C or more,such as about 75°C or more, such as about 80°C or more, such as about 85°C or more, such as about 90°C or more, such as about 93°C or more, such as about 95°C or more, such as about 98°C or more, such as about 100°C or more, such as about 105°C or more, such as about 110°C or more, such as about 120°C or more, such as about 130°C or more. The modified novolak resin may have a particular softening point of about 150°C or less, such as about 140°C or less, such as about 135°C or less, such as about 130°C or less, such as about 125°C or less, such as about 120°C or less, such as about 115°C or less, such as about 110°C or less, such as about 105°C or less, such as about 103°C or less, such as about 101 °C or less, such as about 100°C or less, such as about 99°C or less, such as about 98°C or less, such as about 97°C or less, such as about 96°C or less. The ring and ball softening point may be determined according to ASTM E-28 (Revision 1996) at a heating and cooling rate of 10° C. / min.

[0113] The novolak resin composition may have a particular softening point of about 50°C or more, such as about 60°C or more, such as about 70°C or more, such as about 75°C or more, such as about 80°C or more, such as about 85°C or more, such as about 90°C or more, such as about 93°C or more, such as about 95°C or more, such as about 98°C or more, such as about 100°C or more, such as about 105°C or more, such as about 110°C or more, such as about 120°C or more, such as about 130°C or more. The novolak resin composition may have a softening point of about 150°C or less, such as about 140°C or less, such as about 135°C or less, such as about 130°C or less, such as about 125°C or less, such as about 120°C or less, such as about 115°C or less, such as about 110°C or less, such as about 105°C or less, such as about 103°C or less, such as about 101 °C or less, such as about 100°C or less, such as about 99°C or less, such as about 98°C or less, such as about 97°C or less, such as about 96°C or less. The ring and ball softening point may be determined according to ASTM E-28 (Revision 1996) at a heating and cooling rate of 10° C. / min.

[0114] The modified novolak resin may have a particular glass transition temperature of about 30°C or more, such as about 35°C or more, such as about 40°C or more, such as about 45°C or more, such as about 50°C or more, such as about 55°C or more, such as about 60°C or more, such as about 65°C or more, such as about 70°C or more, such as about. The modified novolak resin may have a glass transition temperature of about 150°C or less, such as about 130°C or less,such as about 110°C or less, such as about 100°C or less, such as about 90°C or less, such as about 85°C or less, such as about 80°C or less, such as about 75°C or less. The glass transition temperature may be determined according to ASTM £1356-08(2014).

[0115] The novolak resin composition may have a particular glass transition temperature of about 30°C or more, such as about 35°C or more, such as about 40°C or more, such as about 45°C or more, such as about 50°C or more, such as about 55°C or more, such as about 60°C or more, such as about 65°C or more, such as about 70°C or more, such as about. The modified novolak resin may have a glass transition temperature of about 150°C or less, such as about 130°C or less, such as about 110°C or less, such as about 100°C or less, such as about 90°C or less, such as about 85°C or less, such as about 80°C or less, such as about 75°C or less. The glass transition temperature may be determined according to ASTM £1356-08(2014).

[0116] The modified novolak resin may have a particular number average molecular weight. For instance, the number average molecular weight may be about 500 g / mol or more, such as about 600 g / mol or more, such as about 700 g / mol or more, such as about 800 g / mol or more, such as about 900 g / mol or more, such as about 1000 g / mol or more, such as about 1100 g / mol or more, such as about 1200 g / mol or more, such as about 1300 g / mol or more, such as about 1500 g / mol or more, such as about 1700 g / mol or more, such as about 2000 g / mol or more. The number average molecular weight may be about 5000 g / mol or less, such as about 4500 g / mol or less, such as about 4000 g / mol or less, such as about 3500 g / mol or less, such as about 3000 g / mol or less, such as about 2800 g / mol or less, such as about 2500 g / mol or less, such as about 2300 g / mol or less, such as about 2100 g / mol or less, such as about 2000 g / mol or less, such as about 1900 g / mol or less, such as about 1800 g / mol or less, such as about 1600 g / mol or less, such as about 1400 g / mol or less, such as about 1200 g / mol or less, such as about 1000 g / mol or less, such as about 800 g / mol or less.

[0117] The novolak resin composition and modified novolak resin as defined herein may be utilized in a wide variety of applications. These may include, but are not limited to, adhesives, dispersants, surfactants, emulsifiers, elastomers, coating, painting, thermoplastic elastomers, engineering resins, ink components, lubricants, polymer blend components, paper additives, biomaterials, watertreatment additives, cosmetics components, antistatic agents, food and beverage packaging materials, release compounding agents in pharmaceuticals applications, etc.

[0118] Particularly, the novolak resin composition and modified novolak resin may be utilized as tackifiers. In particular, they may be utilized as tackifiers for rubber compositions. In this regard, a novolak resin composition (or modified novolak resin) as defined herein may be provided to a rubber.

[0119] The rubber is not necessarily limited. For instance, the rubber may be a natural rubber, a synthetic rubber, or a mixture thereof. Examples of synthetic rubber include, but are not limited to, styrene butadiene copolymer, polyisoprene, polybutadiene, acrylonitrile butadiene styrene, EPDM, polychloroprene, isobutylene, styrene-isoprene-styrene, styrene-butadiene- styrene, ethylene propylene copolymer, nitrile (copolymer of acrylonitrile with butadiene or isoprene), polyurethane, etc. as well as mixtures thereof.Accordingly, the rubber composition itself may include a single rubber or a mixture of rubbers.

[0120] The novolak resin composition may be added to a rubber in an amount of about 0.1 phr or more, such as about 0.2 phr or more, such as about 0.3 phr or more, such as about 0.5 phr or more, such as about 0.7 phr or more, such as about 0.9 phr or more, such as about 1 phr or more, such as about 1.3 phr or more, such as about 1.5 phr or more, such as about 1 .8 phr or more, such as about 2 phr or more, such as about 2.3 phr or more, such as about 2.5 phr or more, such as about 2.8 phr or more, such as about 3 phr or more, such as about 3.3 phr or more, such as about 3.5 phr or more, such as about 3.8 phr or more.The novolak resin composition may be added to a rubber in an amount of about 10 phr or less, such as about 9 phr or less, such as about 8 phr or less, such as about 7 phr or less, such as about 6 phr or less, such as about 5.8 phr or less, such as about 5.5 phr or less, such as about 5.2 phr or less, such as about 5 phr or less, such as about 4.5 phr or less, such as about 4 phr or less, such as about 3.8 phr or less, such as about 3.5 phr or less, such as about 3.2 phr or less, such as about 3 phr or less, such as about 2.8 phr or less, such as about 2.5 phr or less, such as about 2.2 phr or less, such as about 2 phr or less, such as about 1.8 phr or less, such as about 1 .6 phr or less, such as about 1 .4 phr or less, such as about 1 .2 phr or less, such as about 1 phr or less.

[0121] The modified novolak resin may be added to a rubber in an amount of about 0.1 phr or more, such as about 0.2 phr or more, such as about 0.3 phr or more, such as about 0.5 phr or more, such as about 0.7 phr or more, such as about 0.9 phr or more, such as about 1 phr or more, such as about 1 .3 phr or more, such as about 1.5 phr or more, such as about 1 .8 phr or more, such as about 2 phr or more, such as about 2.3 phr or more, such as about 2.5 phr or more, such as about 2.8 phr or more, such as about 3 phr or more, such as about 3.3 phr or more, such as about 3.5 phr or more, such as about 3.8 phr or more. The modified novolak resin may be added to a rubber in an amount of about 10 phr or less, such as about 9 phr or less, such as about 8 phr or less, such as about 7 phr or less, such as about 6 phr or less, such as about 5.8 phr or less, such as about 5.5 phr or less, such as about 5.2 phr or less, such as about 5 phr or less, such as about 4.5 phr or less, such as about 4 phr or less, such as about 3.8 phr or less, such as about 3.5 phr or less, such as about 3.2 phr or less, such as about 3 phr or less, such as about 2.8 phr or less, such as about 2.5 phr or less, such as about 2.2 phr or less, such as about 2 phr or less, such as about 1.8 phr or less, such as about 1 .6 phr or less, such as about 1 .4 phr or less, such as about 1 .2 phr or less, such as about 1 phr or less.

[0122] Furthermore, it should be understood that more than one modified novolak resin as defined herein may be provided to the rubber. Accordingly, a single modified novolak resin as defined herein or a mixture of modified novolak resins as defined herein may be incorporated in the rubber composition.

[0123] The novolak resin composition and modified novolak resin may be provided to an unvulcanized rubber either together or separate from crosslinking agents. Furthermore, other conventional additives may also be utilized in the rubber composition. These may include, but are not limited to, carbon black, fillers, vulcanizing agents, accelerators, activators, processing auxiliaries, etc.

[0124] The rubber composition may be utilized in various applications. For instance, the rubber composition may be utilized to make various articles, such as industrial rubber goods, such as damping elements, rubber sleeves, bellows, conveyor belts, vehicle tires, etc.

[0125] The novolak resin composition and modified novolak resin as defined herein may also be utilized for other applications. For instance, these may include, but are not limited to, friction linings, impregnating agents for organic and / orinorganic fibers, binders for organic and / or inorganic fibers, coatings, finishes and paints and also binders for comminuted, preferably inorganic, materials. In these applications, the novolak resin composition and modified novolak resin can be processed with or without crosslinking agents and also with fillers, additives, pigments, and other added substances and then subjected optionally to one or more subsequent heat treatment processes, optionally with shaping, it also being possible for the temperature to be above the decomposition temperature of the novolak.ExamplesExample 1

[0126] A modified novolak resin was prepared using para-octylphenol (“POP”) as the hydrocarbylphenol, alpha-methylstyrene (“AMS”) as the modifying agent, and formaldehyde as the aldehyde. In the synthesis, POP was charged to a flask and a catalyst (dodecyl benzene sulfonic acid - DDBSA) was added to the flask. The mixture was heated to the reaction temperature. Then, AMS was added over a period of time and then allowed to stir. Next, formaldehyde was dosed over a period of time and the formed water was removed by distillation.After dosing, the reaction was neutralized using triethanolamine (“TEOH”) and the product was discharged.

[0127] The table below provides various reaction conditions as well as the ring and ball softening point, the amount of POP in the final product, and molecular weight characterizations. As can be seen, the amount of POP present in the final product was less than 1 .5 wt.%, in certain examples less than 1 wt.%, and in other examples even less than 0.5 wt.%.

[0128] Table 1. Reaction Conditions and PropertiesExample 2

[0129] A modified novolak resin was prepared using para-octylphenol(“POP”) as the hydrocarbylphenol, alpha-methylstyrene (“AMS”) as the modifying agent, and formaldehyde as the aldehyde. In the synthesis, POP was charged to a flask and a catalyst (dodecyl benzene sulfonic acid - DDBSA) was added to the flask. The mixture was heated to the reaction temperature. Then, AMS was added over a period of time and then allowed to stir. Next, formaldehyde was dosed over a period of time and the formed water was removed by distillation.After dosing, the reaction was neutralized using triethanolamine (“TEOH”) and the product was discharged.

[0130] The table below provides various conditions regarding the synthesis.

[0131] Table 2. Reaction Conditions

[0132] These and other modifications and variations of the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the invention so further described in such appended claims.

Claims

IN THE CLAIMS1 . A method of making a novolak resin composition comprising a modified novolak resin, the method comprising: providing a mixture comprising a hydrocarbylphenol and a vinyl compound modified hydrocarbylphenol; and reacting an aldehyde and / or ketone with the hydrocarbylphenol in the presence of the vinyl compound modified hydrocarbylphenol to form the modified novolak resin wherein at least one end of the modified novolak resin is formed from the vinyl compound modified hydrocarbylphenol.

2. A novolak resin composition comprising a modified novolak resin formed by a method comprising: providing a mixture comprising a hydrocarbylphenol and a vinyl compound modified hydrocarbylphenol; and reacting an aldehyde and / or ketone with the hydrocarbylphenol in the presence of the vinyl compound modified hydrocarbylphenol to form the modified novolak resin wherein at least one end of the modified novolak resin is formed from the vinyl compound modified hydrocarbylphenol.

3. A rubber composition comprising: a rubber and the novolak resin composition of claim 2.

4. A method of making a novolak resin composition comprising a modified novolak resin, the method comprising: providing a mixture comprising a hydrocarbylphenol and a vinyl compound modifying agent and / or a dimer thereof; reacting a portion of the hydrocarbylphenol and the vinyl compound modifying agent and / or a dimer thereof to form a vinyl compound modified hydrocarbylphenol; and reacting an aldehyde and / or ketone with the hydrocarbylphenol in the presence of the vinyl compound modified hydrocarbylphenol to form the modified novolak resin wherein at least one end of the modified novolak resin is formed from the vinyl compound modified hydrocarbylphenol.

5. A novolak resin composition comprising a modified novolak resin formed by a method comprising: providing a mixture comprising a hydrocarbylphenol and a vinyl compound modifying agent and / or a dimer thereof;reacting a portion of the hydrocarbylphenol and the vinyl compound modifying agent and / or a dimer thereof to form a vinyl compound modified hydrocarbylphenol; and reacting an aldehyde and / or ketone with the hydrocarbylphenol in the presence of the vinyl compound modified hydrocarbylphenol to form the modified novolak resin wherein at least one end of the modified novolak resin is formed from the vinyl compound modified hydrocarbylphenol.

6. A rubber composition comprising: a rubber and the novolak resin composition of claim 5.

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