Alkylphenol resins and a method of preparing thereof
View Patent ↗Compositions, methods, and resins using alkyl aldehydes and phenols are provided herein. In one embodiment, a composition comprising an alkylphenol resin can be prepared by condensing at least one phenolic monomer selected from the group consisting of phenol, cresol, resorcinol, xylenol, ethyl phenol, alkylresorcinols, and combinations thereof; and at least one alkyl aldehyde having from 5 to 12 carbon atom alkyl groups. The alkylphenol resins of the application are free of octylphenol or nonylphenol monomers. In one embodiment, the alkylphenol resins may be prepared using formaldehyde, and alternatively, in another embodiment, the alkylphenol resins may be prepared without the use of formaldehyde. The process to make these new alternative alkylphenol resins is a cost effective process and easy to scale-up.
1. A method for making an alkylphenol resin, comprising:
adding at least one phenolic monomer selected from the group consisting of phenol, cresol, resorcinol, xylenol, ethyl phenol, alkyl resorcinols, and combinations thereof and at least one alkyl aldehyde having from 5 to 12 carbon atoms in the presence of an acid catalyst to form a first reaction mixture;
adding a base catalyst and formaldehyde to the first reaction mixture to form a second reaction mixture;
reacting the second reaction mixture at conditions sufficient to form a reaction product comprising at least one alkylphenol resin; and
performing a reflux or azeotropic distillation process to recover the at least one alkylphenol resin, wherein the at least one alkylphenol resin has a molecular weight of 2,000 Daltons to 50,000 Daltons and a relative solubility number (RSN) of about 7.5 to about 12.5.
2. The method of claim 1 , wherein the alkylphenol resin acts as a tackifier.
3. The method of claim 1 , wherein the alkyl aldehyde is selected from the group consisting of 3,5,5-trimethyl hexanal, nonanal, 2-ethyl hexanal, and combinations thereof.
4. The method of claim 1 , wherein the alkyl resorcinols comprise dihydroxy benzenes having one or two alkyl chains present on a ring.
5. The method of claim 4 , wherein the alkyl chains present on the ring comprise from 1 to 3 carbons.
6. A rubber composition, comprising the alkylphenol resin of claim 1 , wherein the alkylphenol resin is present in the composition in the range of from 1 to 10 parts per hundred rubber.
7. The method of claim 1 , wherein a ratio of the at least one alkyl aldehyde to the at least one phenolic monomer is 0.5 to 1.0.
8. The method of claim 1 , wherein the reflux or azeotropic distillation process comprises a temperature from 100° C. to 140° C.
9. The method of claim 1 , further comprising providing a solvent with the at least one phenolic monomer.
10. The method of claim 1 , wherein the reacting the second mixture is performed in the presence of an organic solvent that forms an azeotrope with water.
11. The method of claim 1 , wherein a ratio of the at least one alkyl aldehyde to the at least one phenolic monomer is greater than 1.0.
12. The method of claim 1 , wherein the formaldehyde is added before the base catalyst.
13. The method of claim 1 , wherein the formaldehyde is added after the base catalyst.
14. A method for making an alkylphenol resin, comprising:
mixing at least one phenolic monomer, at least one alkyl aldehyde having from 5 to 12 carbon atoms, formaldehyde, at least one acid catalyst, and at least one base catalyst to provide a reaction mixture comprising the at least one phenolic monomer, at least one alkyl aldehyde having from 5 to 12 carbon atoms, formaldehyde, at least one acid catalyst, and at least one base catalyst, wherein:
the at least one phenolic monomer is selected from the group consisting of phenol, cresol, resorcinol, xylenol, ethyl phenol, and alkyl resorcinols; and
the acid catalyst is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids haloacetic acids, and combinations thereof, to form an intermediate product;
reacting the reaction mixture at conditions sufficient to form a reaction product comprising at least one alkylphenol resin; and
distilling the reaction product to recover the at least one alkylphenol resin, wherein the at least one alkylphenol resin has a molecular weight of 2,000 Daltons to 50,000 Daltons and a relative solubility number (RSN) of about 7.5 to about 12.5.
15. The method of claim 14 , wherein the at least one alkylphenol resin is a resole.
16. The method of claim 14 , wherein the at least one alkylphenol resin is a novolac.
17. The method of claim 14 , wherein the reaction mixture further comprises an organic solvent selected from the group of an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent or combination therein.
18. The method of claim 14 , wherein a mole ratio of the formaldehyde to the at least one phenolic monomers is about 0.25:1 to about 1.25:1.
19. A method for making an alkylphenol resin, comprising:
mixing at least one phenolic monomer, at least one alkyl aldehyde having from 5 to 12 carbon atoms, formaldehyde, at least one acid catalyst, at least one base catalyst, and an organic solvent to provide a reaction mixture comprising the at least one phenolic monomer, at least one alkyl aldehyde having from 5 to 12 carbon atoms, formaldehyde, at least one acid catalyst, at least one base catalyst and organic solvent, wherein:
the at least one phenolic monomer is selected from the group consisting of phenol, cresol, resorcinol, xylenol, ethyl phenol, and alkyl resorcinols;
the acid catalyst is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids haloacetic acids, and combinations thereof, to form an intermediate product;
the organic solvent is selected from the group consisting of an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent or a combination thereof;
the reaction mixture comprises less than 5 wt % of octylphenol and nonylphenol monomers, based on the total weight of the at least one phenolic monomer; and
a mole ratio of the formaldehyde to the at least one phenolic monomers is about 0.25:1 to about 1.25:1,
reacting the reaction mixture at conditions sufficient to form a reaction product comprising at least one alkylphenol resin; and
distilling the reaction product to provide a condensate product comprising the at least one alkylphenol resin, wherein the at least one alkylphenol resin has a molecular weight of 2,000 Daltons to 50,000 Daltons and a relative solubility number (RSN) of about 7.5 to about 12.5, and wherein the reaction product is free of formaldehyde.
20. The method of claim 19 , wherein the at least one alkylphenol resin is a resole or a novolac.