Compositions and process for stabilizing phenolic resins containing calixarenes

Patent metadata

Field	Value
Publication number	US-2018208701-A1
Application number	US-201815879245-A
Country	US
Kind code	A1
Filing date	Jan 24, 2018
Priority date	Jan 25, 2017
Publication date	Jul 26, 2018
Grant date	—

Abstract

This invention relates to compositions and a process for stabilizing or solubilize a phenolic resin containing a mixture of linear phenolic resins and calixarenes. The process comprises contacting the phenolic resin with an epoxide, to at least partially alkoxylate the phenolic hydroxyl groups of the calixarenes. This process forms a stabilized or solubilized phenolic resin with an increased solubility in a hydrocarbon solvent.

First claim

We claim:

1 . A resin solution of a phenolic resin, comprising one or more modified calixarene compounds, each calixarene compound comprising 4-20 units of formula (I′) and/or formula (II):

wherein:
each X is independently the same or different moiety, each moiety having a structure of

each R 1 is independently a H, C 1 to C 30 alkyl, phenyl, or arylalkyl;
each R 2 is independently a H, C 1 to C 20 branched or unbranched alkyl which may optionally be substituted with one or more glycidyl ether units of the formula

C 2 to C 10 alkenyl, or C 5 to C 10 aryl;
each L is independently selected from the group consisting of —CH 2 —, —C(O)—, —CH(R 3 )—, —(CH 2 ) n —O—(CH 2 ) n —, —C(R 3 ) 2 —, and —S—;
each R 3 is independently a C 1 -C 6 alkyl;
each m is independently an integer from 0 to 10;
each n is independently an integer from 1 to 2;
each q is independently an integer from 1 to 100;
each A 1 represents a direct covalent bond to an adjacent unit of formula (I′) or formula (II) such that there is one L group between adjacent units, whereby the total units in the calixarene compound form a ring; and
wherein units of formula (I′) make up from about 35% to 100% of the overall units present in the calixarene compound, and
wherein the phenolic resin is soluble in a hydrocarbon solvent having a concentration of about 50 wt % to about 75 wt %.

2 . The resin solution of claim 1 , wherein each m is 0 or 1.

3 . The resin solution of claim 2 , wherein each R 2 is independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, allyl, ethylhexyl, octyl, nonyl, decyl, phenyl, nonylphenyl, and hexadecyl; or is independently a C 1 to C 20 branched or unbranched alkyl substituted with one or more glycidyl ether units of the formula

4 . The resin solution of claim 3 , wherein each R 2 is n-butyl or

5 . The resin solution of claim 2 , wherein each R 1 is independently a C 4 to C 12 alkyl or C 24 to C 28 alkyl.

6 . The resin solution of claim 2 , wherein the total number of units in the calixarene compounds is from 4 to 8.

7 . The resin solution of claim 1 , wherein q is 1 in one or more units in the modified calixarene compounds.

8 . The resin solution of claim 1 , wherein the one or more modified calixarene compounds have one or more units of formula (I′) represented by the structure of

wherein:
each R 1 is independently a C 4 to C 12 alkyl;
each L is independently selected from the group consisting of —CH 2 —, —C(O)—, —CH(R 3 )—, —(CH 2 ) n —O—(CH 2 ) n —, and —C(R 3 ) 2 —;
each R 3 is independently a C 1 -C 6 alkyl;
each n is independently an integer from 1 to 2; and
the total number of units in the calixarene compounds is from 4 to 8.

9 . The resin solution of claim 8 , wherein each R 1 is independently tert-butyl, nonyl, or tert-octyl.

10 . The resin solution of claim 1 , wherein the hydrocarbon solvent is an aromatic hydrocarbon solvent selected from the group consisting of toluene, xylene, tetralin, a C 9 -C 10 aromatic hydrocarbon solvent, and a C 10 -C 12 aromatic hydrocarbon solvent.

11 . A resin with an increased solubility in a hydrocarbon solvent, comprising one or more modified calixarene compounds, each calixarene compound comprising 4-20 units of formula (I′) and/or formula (II):

wherein:
each X is independently the same or different moiety, each moiety having a structure of

each R 1 is independently a H, C 1 to C 30 alkyl, phenyl, or arylalkyl;
each R 2 is independently a H, C 1 to Co branched or unbranched alkyl which may optionally be substituted with one or more glycidyl ether units of the formula

C 2 to C 10 alkenyl, or C 5 to C 10 aryl;
each L is independently selected from the group consisting of —CH 2 —, —C(O)—, —CH(R 3 )—, —(CH 2 ) n —O—(CH 2 ) n —, —C(R 3 ) 2 —, and —S—;
each R 3 is independently a C 1 -C 6 alkyl;
each m is independently an integer from 0 to 10;
each n is independently an integer from 1 to 2;
each q is independently an integer from 1 to 100;
each A 1 represents a direct covalent bond to an adjacent unit of formula (I′) or formula (II) such that there is one L group between adjacent units, whereby the total units in the calixarene compound form a ring; and
wherein units of formula (I′) make up from about 35% to 100% of the overall units present in the calixarene compound, and
wherein the solubility of the resin is increased by at least 20% compared to a resin comprising calixarene compounds containing units of formula (II) but no units of formula (I′).

12 . A process for stabilizing or solubilizing a phenolic resin mixture, comprising:
reacting a phenolic resin mixture comprising linear phenolic resins and calixarene compounds having pendant phenolic hydroxyl groups with one or more compounds of formula (III):

an optional catalyst, and at least one hydrocarbon solvent at an elevated temperature for a period of time sufficient to alkoxylate one or more of the phenolic hydroxyl groups of the linear phenolic resins and/or calixarene compounds in the phenolic resin mixture to result in a resin solution substantially free of undissolved solid components, wherein the solubility of the phenolic resin mixture is increased by at least 20% compared to a phenolic resin mixture that is not subjected to said reacting step, wherein
R 2 is a H, C 1 to C 20 branched or unbranched alkyl which may optionally be substituted with one or more glycidyl ether units of the formula

C 2 to C 10 alkenyl, or C 5 to C10 aryl; and
m is an integer from 0 to 10.

13 . The process of claim 12 , wherein, on average, about 0.1 to about 20 moles of the compounds of formula (III) are added to react with each mole of the phenolic units of the phenolic resin.

14 . The process of claim 12 , wherein the catalyst is present and is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, imidazole, 2-methylimidazole, pyridine, and combinations thereof.

15 . The process of claim 12 , wherein the elevated temperature is in the range of 110-170° C.

16 . The process of claim 12 , wherein less than 5% of residual compound of formula (III) remains unreacted within 1 hour of the addition of the compound of formula (III).

Assignees

• Si Group Inc

Inventors

• Biittig Ricky
• Meketa Matthew

Classifications

• C08L61/14

  Modified phenol-aldehyde condensates · CPC title

• B01D17/047

  with separation aids · CPC title

• C08G8/36 Primary

  by etherifying · CPC title

• C10G2300/1033

  Oil well production fluids · CPC title

• C08G8/12

  with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol · CPC title