Phenolic resin polyols and polymers derived from the polyols

Details Phenolic resin polyols and polymers derived from the polyols Phenolic resin polyols and polymers derived from the polyols

1999-05-26

2003-05-27

Mullis, Jeffrey (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S394000, C525S395000, C525S396000, C525S397000, C525S461000, C525S523000, C525S529000

Reexamination Certificate

active

06569953

ABSTRACT:

FIELD OF THE INVENTION
The invention relates to phenolic resin polyols and their preparation by oxyalkylation. The phenolic resin polyols of the invention have aliphatic or mixed aliphatic/phenolic hydroxyl groups, which makes them versatile intermediates for a broad range of polymer systems, including urethanes, epoxies, alkyds, acrylates, and polyesters.
BACKGROUND OF THE INVENTION
A new class of phenol aralkylation polymers was recently described. These polymers exhibit improved oil solubility, improved compatibility with oil and alkyd-based polymers, urethanes, and epoxies, and a decreased tendency to form color bodies that darken coatings derived from the phenol aralkylation polymers. One way to make the phenol aralkylation polymers is to first aralkylate a phenolic monomer (such as bisphenol A) with a styrene derivative to obtain an aralkylated phenol, and then react the aralkylated phenol with an aryl diolefin to produce the phenol aralkylation polymer. This reaction scheme is illustrated in the simplified scheme below:
As those skilled in the art will appreciate, these polymers are actually complex mixtures that contain many structural analogs of the compounds pictured above. The types of structures actually present, of course, depend greatly upon the relative proportions of phenolic monomer, styrene derivative, and aryl diolefin.
Phenol aralkylation polymers can be made by first reacting the phenolic monomer with an aryl diolefin to obtain a phenovaryl diolefin polymer, and then aralkylating the phenol/aryl diolefin polymer with a styrene derivative to obtain a phenol aralkylation polymer. In this case, the phenolic component is joined to the aryl diolefin with at least a portion of the phenolic linkages para to the phenolic hydroxyl groups. This process, which produces a phenol aralkylation polymer having a higher melting point, is shown in the simplified scheme below:
The phenol aralkylation polymers described above have many advantages compared with standard phenolics, including good solubility, good compatibility, and low discoloration. Improved solubility in nonpolar solvents is a direct consequence of styrene component addition, as is the improved compatibility with other typical resin systems, including epoxies, acrylates, styrenics, and the like. Lower rates of discoloration compared with phenolics result from the absence of dihydromethylene linkages.
The usefulness of phenol aralkylation polymers, however, is somewhat limited by the presence of only phenolic hydroxyl groups. For example, the usefulness of phenol aralkylation polymers in the coating and adhesive product areas is limited by the inability of phenolic hydroxyl groups to react either with organic acids to form esters, or with esters to form new esters by transesterification. The esterification and transesterification reactions require aliphatic hydroxyl groups. In addition, phenol aralkylation polymers having only phenolic hydroxyl groups will not react with maleic anhydride to produce unsaturated polyesters. In sum, although the limited reactivity of phenol aralkylation polymers does not preclude their use in coatings and adhesives, it does restrict their usefulness in these applications.
SUMMARY OF THE INVENTION
The invention is a phenolic resin polyol. The phenolic resin polyol is the reaction product of an aralkylated phenol or a phenol aralkylation polymer with an oxyalkylating agent selected from alkylene oxides and alkylene carbonates. Unlike either the aralkylated phenol or phenol aralkylation polymer, the phenolic resin polyol contains at least some aliphatic hydroxyl groups.
The invention includes a process for making phenolic resin polyols. The process comprises reacting an aralkylated phenol or a phenol aralkylation polymer with an oxyalkylating agent selected from alkylene oxides and alkylene carbonates in the presence of an oxyalkylation catalyst under conditions effective to produce the phenolic resin polyol.
Reaction with an alkylene carbonate adds a single oxyalkylene unit, and effectively converts a phenolic hydroxyl group to an aliphatic hydroxyl group. When an alkylene oxide is used, multiple oxyalkylene units can be added. This allows the solubility and compatibility characteristics of the phenolic resin polyols to be adjusted for a particular end use. With either type of oxyalkylating agent, the relative proportion of phenolic and aliphatic hydroxyl groups can be adjusted easily, so a formulator has great flexibility and control over polyol reactivity.
The phenolic resin polyols are exceptionally useful in preparing a wide variety of polymer systems. Like phenol aralkylation polymers, they react, for example, with melamine resins to produce melamine-linked polymers, with di- or polyisocyanates or isocyanate-terminated prepolymers to make polyurethanes, or with epoxy resins to make epoxy thermosets. Unlike phenol aralkylation polymers, the phenolic resin polyols of the invention also react with diacids or polyacids to make polyesters, with fatty acids or fatty esters to make alkyds, and with acrylic acids or esters to make curable acrylate compositions. In sum, we found that incorporation of aliphatic hydroxyl groups into these phenolic polymers expands their usefulness in polymer systems, yet still maintains the advantages of phenol aralkylation polymers in many systems.
DETAILED DESCRIPTION OF THE INVENTION
The phenolic resin polyols of the invention are the reaction products of an aralkylated phenol or a phenol aralkylation polymer with an oxyalkylating agent selected from alkylene oxides and alkylene carbonates.
“Aralkylated phenols” useful in the invention are made by aralkylating a phenolic monomer with at least one styrene derivative. A typical reaction is shown below:
“Phenol aralkylation polymers” useful in the invention derive from a phenolic monomer, at least one styrene derivative, and a coupling agent, which is typically an aryl diolefin. Mixtures of different phenolic monomers, styrene derivatives, or coupling agents can be used to modify physical properties.
Phenol aralkylation polymers are produced by a process that has at least two steps. The reaction sequence is controlled to provide phenol aralkylation polymers that have the desired properties. In one process, a phenolic monomer reacts with at least one styrene derivative to produce an aralkylated phenol. The aralkylated phenol then reacts with a coupling agent, preferably an aryl diolefin, to produce the phenol aralkylation polymer. A second process reacts the phenolic monomer first with the coupling agent, and then with the styrene derivative to produce the phenol aralkylation polymer. Both of these processes are illustrated in the Background section. In either process, part of the styrene derivative or coupling agent can be withheld for later reaction to modify performance characteristics of the phenol aralkylation polymer.
The aralkylated phenols or phenol aralkylation polymers described above react with an oxyalkylating agent selected from alkylene oxides and alkylene carbonates in the presence of an oxyalkylation catalyst under conditions effective to produce phenolic resin polyols of the invention.
Phenolic monomers useful in the invention include phenols that have at least two free “reactive” positions, i.e., two aromatic C—H bonds that are activated for electrophilic aromatic substitution. In other words, the phenolic monomers have at least two aromatic C—H groups in positions either ortho or para to a phenolic hydroxyl group. Phenol, for example, has three free reactive positions: two ortho and one para to the phenolic hydroxyl group.
The phenols may be substituted with one or more C
1
-C
20
alkyl, aryl, or aralkyl substituents, provided that at least two reactive positions remain. Suitable substituted phenols include, for example, o-cresol, m-cresol, p-cresol, m-isopropyl phenol, 3,5-xylenol, 3,5-diisopropylphenol, p-t-butylphenol, and the like, and mixtures thereof. Suitable phenols include those having more than one phenolic hydroxyl group, such as hydroquinone, resorcinol, catechol, and C

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