US4264671A — Phenol formaldehyde resoles and laminates

Claim 1

Independent Claim 142 words

A process for forming a heat-curable, phenol-formaldehyde glass fiber prepreg, including a glass fiber substrate, comprising: saturating said substrate with a phenol-formaldehyde resin characterized by a formaldehyde to phenol ratio of 1.9-5.0:1 and by carbon-13 nuclear magnetic resonance sprectra as having at least 30% by weight benzyl formal groups of the form Ph--(CH 2 O) n --CH 2 OH, n≧1, less than about 20% by weight methylene groups of the form Ph--CH 2 --Ph and less than about 40% by weight methylol groups of the form Ph--CH 2 OH, wherein Ph is a phenol nucleus; squeezing said saturated substrate until the desired level of resin is contained in the web, and; heating said matrix at 110°-140° C. until a desired level of resin content is fixed in the web and the concentration of volatile materials remaining does not exceed 1.5 weight percent.

Claim 2

Dependent Claim 142 words

A process for forming a heat-curable, phenol-formaldehyde glass fiber prepreg, including a glass fiber substrate, comprising: saturating said substrate with a phenol-formaldehyde resin characterized by a formaldehyde to phenol ratio of 1.9-5.0:1 and by carbon-13 nuclear magnetic resonance sprectra as having at least 30% by weight benzyl formal groups of the form Ph--(CH 2 O) n --CH 2 OH, n≧1, less than about 20% by weight methylene groups of the form Ph--CH 2 --Ph and less than about 40% by weight methylol groups of the form Ph--CH 2 OH, wherein Ph is a phenol nucleus; squeezing said saturated substrate until the desired level of resin is contained in the web, and; heating said matrix at 110°-140° C. until a desired level of resin content is fixed in the web and the concentration of volatile materials remaining does not exceed 1.5 weight percent.

Claim 3

Dependent Claim 9 words

The heat-curable phenol-formaldehyde resin-glass fiber prepreg of claim 1.

Claim 4

Dependent Claim 31 words

The process of claim 1 wherein said resin is characterized by a formaldehyde to phenol ratio of 1.9-2.75:1 and the process cure temperature is 110°-125° C. for at least 2.0 minutes.

Claim 5

Dependent Claim 32 words

The process of claim 1, wherein said resin is characterized by formaldehyde to phenol ratio of about 2.75-3.5:1, and the process cure temperature is 125°-140° C. for at least about 2.0 minutes.

Claim 6

Dependent Claim 115 words

The process of claim 1 wherein the product of said process is formed into a fire-resistant phenol-formaldehyde resin-glass fiber laminate by additional processing steps, comprising: shaping the heat-curable phenol-formaldehyde resin-glass fiber prepreg of claim 1 into single sheets; assembling a plurality of said sheets into a precure laminate; pressing said precure laminate at contact pressure of about 2-15 psig; heating said precure laminate, simultaneously with pressing at contact pressure, to about 100°-130° C. for at least about 10 minutes; pressing said precured laminate at greater than contact pressures, in the range of 15-200 psig; heating said laminate, simultaneously with pressing, to about 100°-140° C. until the laminate is cured to a uniform, insoluble, infusible state.

Claim 7

Dependent Claim 8 words

The heat-curable phenol-formaldehyde resin-glass laminate of claim 5.

Claim 8

Dependent Claim 111 words

A phenol-formaldehyde resin, comprising: formaldehyde to phenol molar ratios of about 1.9-5:1, characterized by carbon-13 nuclear magnetic resonance spectra as benzyl formal groups, of the formula Ph--(CH.sub.2 O).sub.n CH.sub.2 OH wherein n≧1, which includes at least about 30 molar percent of the total formaldehyde content of resin; methylene groups, of the formula Ph--CH.sub.2 --Ph which includes less than about 20 molar percent of the formaldehyde content of the resin; and methylol groups, of the formula Ph--CH.sub.2 OH which includes less than about 40 molar percent of the formaldehyde content of the resin, wherein PH-- is a phenol nucleus, said resin capable of curing at 130°-150° C. to an infusible, cross-linked solid.

Claim 9

Dependent Claim 111 words

A phenol-formaldehyde resin, comprising: formaldehyde to phenol molar ratios of about 1.9-5:1, characterized by carbon-13 nuclear magnetic resonance spectra as benzyl formal groups, of the formula Ph--(CH.sub.2 O).sub.n CH.sub.2 OH wherein n≧1, which includes at least about 30 molar percent of the total formaldehyde content of resin; methylene groups, of the formula Ph--CH.sub.2 --Ph which includes less than about 20 molar percent of the formaldehyde content of the resin; and methylol groups, of the formula Ph--CH.sub.2 OH which includes less than about 40 molar percent of the formaldehyde content of the resin, wherein PH-- is a phenol nucleus, said resin capable of curing at 130°-150° C. to an infusible, cross-linked solid.

Claim 10

Dependent Claim 172 words

A phenol-formaldehyde resin, comprising: a water-dilutable condensation product of formaldehyde and phenol in the molar ratios of 2.0-3.2:1, said resin curable to an insoluble cross-linked, infusible solid at 130°-150° C., wherein the formaldehyde content of the resin, prior to curing, characterized by carbon-13 nuclear magnetic resonance spectra, is bound to and distributed among phenol nuclei of the resin as formal groups of the form Ph--(CH.sub.2 --O).sub.n --CH.sub.2 --OH n≧1, in an amount of about 30-40 molar percent of the total formaldehyde content of the resin; ether groups of the form Ph--CH.sub.2 --O--CH.sub.2 --Ph in an amount of about 5-10 molar percent; methylol groups of the form Ph--CH.sub.2 OH in an amount of about 9-40 molar percent; methylene groups of the form Ph--CH.sub.2 --Ph in an amount of about 10-20 molar percent; and free formaldehyde in an amount of about 10-20 molar percent wherein Ph indicates a phenol nucleus and the percentages indicated are the percent of the indicated group with respect to the total moles of formaldehyde charged to the resin system.

Claim 11

Dependent Claim 172 words

A phenol-formaldehyde resin, comprising: a water-dilutable condensation product of formaldehyde and phenol in the molar ratios of 2.0-3.2:1, said resin curable to an insoluble cross-linked, infusible solid at 130°-150° C., wherein the formaldehyde content of the resin, prior to curing, characterized by carbon-13 nuclear magnetic resonance spectra, is bound to and distributed among phenol nuclei of the resin as formal groups of the form Ph--(CH.sub.2 --O).sub.n --CH.sub.2 --OH n≧1, in an amount of about 30-40 molar percent of the total formaldehyde content of the resin; ether groups of the form Ph--CH.sub.2 --O--CH.sub.2 --Ph in an amount of about 5-10 molar percent; methylol groups of the form Ph--CH.sub.2 OH in an amount of about 9-40 molar percent; methylene groups of the form Ph--CH.sub.2 --Ph in an amount of about 10-20 molar percent; and free formaldehyde in an amount of about 10-20 molar percent wherein Ph indicates a phenol nucleus and the percentages indicated are the percent of the indicated group with respect to the total moles of formaldehyde charged to the resin system.

Claim 12

Dependent Claim 227 words

A process for making a low-color, substantially water-dilutable phenol-formaldehyde resin intermediate that cures, without adding additional formaldehyde, to an insoluble, infusible solid at 130°-150° C., comprising: mixing phenol, water and 0.5-2.2 moles per 100 moles of phenol of an alkali catalyst material, wherein the pH of the reaction mixtures is 7.0-10.9; adding formaldehyde to the reaction mixture such that the ratio of formaldehyde to phenol is about 1.9-5.0:1; heating said reaction mixture to reflux temperature, with stirring, at a uniform rate over about a 1-hour period; refluxing said mixture until a viscosity of about 400-2600 centipoise at 50-75% resin solids content is attained; cooling the reaction mixture; and adjusting the pH of the mixture with an acid to a pH of 3.0-6.0 wherein the resulting resin intermediate, characterized by carbon-13 nuclear magnetic resonance spectra, includes formaldehyde bound to and distributed among phenol nuclei of the resin as benzyl formal groups, of the formula Ph--(CH.sub.2 O).sub.n CH.sub.2 OH wherein n≧1, which includes at least about 30 molar percent of the total formaldehyde content of the resin; methylene groups of the formula Ph--CH.sub.2 --Ph which includes less than about 20 molar percent of the total formaldehyde content of the resin, and methylol groups, of the formula Ph--CH.sub.2 OH which includes less than about 40 molar percent of the formaldehyde content of the resin, wherein Ph-- is a phenol nucleus.

Claim 13

Dependent Claim 227 words

A process for making a low-color, substantially water-dilutable phenol-formaldehyde resin intermediate that cures, without adding additional formaldehyde, to an insoluble, infusible solid at 130°-150° C., comprising: mixing phenol, water and 0.5-2.2 moles per 100 moles of phenol of an alkali catalyst material, wherein the pH of the reaction mixtures is 7.0-10.9; adding formaldehyde to the reaction mixture such that the ratio of formaldehyde to phenol is about 1.9-5.0:1; heating said reaction mixture to reflux temperature, with stirring, at a uniform rate over about a 1-hour period; refluxing said mixture until a viscosity of about 400-2600 centipoise at 50-75% resin solids content is attained; cooling the reaction mixture; and adjusting the pH of the mixture with an acid to a pH of 3.0-6.0 wherein the resulting resin intermediate, characterized by carbon-13 nuclear magnetic resonance spectra, includes formaldehyde bound to and distributed among phenol nuclei of the resin as benzyl formal groups, of the formula Ph--(CH.sub.2 O).sub.n CH.sub.2 OH wherein n≧1, which includes at least about 30 molar percent of the total formaldehyde content of the resin; methylene groups of the formula Ph--CH.sub.2 --Ph which includes less than about 20 molar percent of the total formaldehyde content of the resin, and methylol groups, of the formula Ph--CH.sub.2 OH which includes less than about 40 molar percent of the formaldehyde content of the resin, wherein Ph-- is a phenol nucleus.

Claim 14

Dependent Claim 27 words

The process of claim 9 wherein said alkali catalyst material is selected from the group consisting of hydroxides and carbonates of lithium, sodium, potassium, magnesium and calcium.

Claim 15

Dependent Claim 27 words

The process of claim 9 wherein the alkali catalyst is 0.5-1.5 moles of catalyst per 100 moles of phenol, resulting in a reaction mixture pH of 7.1-8.2.

Claim 16

Dependent Claim 11 words

The process of claim 11 wherein said catalyst is lithium carbonate.

Claim 17

Dependent Claim 18 words

The process of claim 9 wherein said adjusting acid step is to a pH range of about 4-5.

Claim 18

Dependent Claim 219 words

A process for making a low-color, substantially water-dilutable phenol-formaldehyde resin intermediate, suitable for making resin-glass cloth laminates, comprising: mixing phenol, water and 0.5-1.5 moles lithium carbonate catalyst per 100 moles of phenol wherein the pH of the mixture is 7.2-6.2; adding formaldehyde to the reaction mixture so that the ratio of formaldehyde to phenol is about 2.0-3.2:1; heating said mixture to reflux temperature, at about 100°-115° C. at atmospheric pressure, with stirring, over a period of about 1 hour; refluxing said mixture until a viscosity of about 400-500 centipoise, at 60-75% by weight resin solids content, is attained; cooling said mixture; and neutralizing said mixture with citric acid to a final pH of 4.0-5.0 wherein said finished intermediate resin, characterized by carbon-13 nuclear magnetic resonance spectra, includes formaldehyde bound to and distributed among phenol nuclei of the resin as benzyl formal groups, of the formua Ph--(CH.sub.2 O).sub.n CH.sub.2 OH n≧1 which includes at least about 30 molar percent of the total formaldehyde content of the resin, methylene groups of the formula Ph--CH.sub.2 --Ph which includes less than about 20 molar percent of the total formaldehyde content of the resin, and methylol groups, of the formula Ph--CH.sub.2 OH which includes less than about 40 molar percent of the total formaldehyde content of the resin, wherein Ph-- is in phenol nucleus.

Claim 19

Dependent Claim 219 words

A process for making a low-color, substantially water-dilutable phenol-formaldehyde resin intermediate, suitable for making resin-glass cloth laminates, comprising: mixing phenol, water and 0.5-1.5 moles lithium carbonate catalyst per 100 moles of phenol wherein the pH of the mixture is 7.2-6.2; adding formaldehyde to the reaction mixture so that the ratio of formaldehyde to phenol is about 2.0-3.2:1; heating said mixture to reflux temperature, at about 100°-115° C. at atmospheric pressure, with stirring, over a period of about 1 hour; refluxing said mixture until a viscosity of about 400-500 centipoise, at 60-75% by weight resin solids content, is attained; cooling said mixture; and neutralizing said mixture with citric acid to a final pH of 4.0-5.0 wherein said finished intermediate resin, characterized by carbon-13 nuclear magnetic resonance spectra, includes formaldehyde bound to and distributed among phenol nuclei of the resin as benzyl formal groups, of the formua Ph--(CH.sub.2 O).sub.n CH.sub.2 OH n≧1 which includes at least about 30 molar percent of the total formaldehyde content of the resin, methylene groups of the formula Ph--CH.sub.2 --Ph which includes less than about 20 molar percent of the total formaldehyde content of the resin, and methylol groups, of the formula Ph--CH.sub.2 OH which includes less than about 40 molar percent of the total formaldehyde content of the resin, wherein Ph-- is in phenol nucleus.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1984-04-27	1984-10-27	1985-04-28	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1988-04-27	1988-10-27	1989-04-28	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1992-04-27	1992-10-27	1993-04-28	$7700.00	Window Closed / Lapsed

Phenol formaldehyde resoles and laminates

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