2,6-bis(hydroxymethyl)-4-methylphenol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A phenolic resin rich in alternating phenolic copolymer block segments was formed by reacting a mixture of 519.0 g of 99 percent pure m-cresol, 538.2 g of 97 percent pure 2,6-bis-(hydroxymethyl)-p-cresol and 20 g oxalic acid dihydrate in a solvent mixture of 40 ml deionized water and 200 ml ethyl cellosolve acetate. The reaction mixture was heated to about 70° C. to initiate the reaction forming the copolymer block segments. At 102° C., 32.6 g of 36.9 percent formaldehyde was added in 8 minutes to the reaction mixture to form substantially m-cresol formaldehyde block segments and to chemically bond these segments to the previously formed copolymer blocks. After heating the mixture at reflux for three hours, the amount of heat was increased to remove the water and solvent by distillation. When the temperature of the reaction mixture reached about 220° C., a partial vacuum was applied and was gradually increased to 4 mm Hg to remove the unreacted monomers. Maximum mixture temperature during vacuum stripping was about 226° C. The copolymer was poured from the reaction kettle and allowed to cool. About 840 g of product having a Tg of 112° C. was obtained. was formed in a solvent mixture of 40 ml forming the copolymer block segments

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 1 liter, 3 necked round bottomed flask equipped with a paddle stirrer, condenser, thermometer and heating source, were added 159 g (1.45 moles) of catechol, 10 g (0.11 moles) of oxalic acid and 100 g of water. The mixture was stirred and heated to 60° C. Complete solution was obtained. 147 g (0.874 moles) of 2,6-bis(hydroxymethyl)-4-methylphenol were added, in eight equal portions. After the first portion was added, the temperature dropped several degrees. The temperature of the reaction mixture was raised to 70° C. and four more portions were added at 15 minute intervals. After five portions were added, the temperature of the reaction was raised to 80° C. and the remaining three portions were added at 15 minute intervals. The reaction product phase separated, with the water layer on top. The temperature was then raised to 110° C. and held for 10 minutes. The temperature was then raised to 185° C. and held for 15 minutes. Vacuum was gradually applied and ultimately brought to 30 mm Hg. The reaction mixture was held under these conditions for 30 minutes. The vacuum was broken and the hot product drained into an aluminum dish. After cooling, a dark brown, brittle solid was obtained. 13C NMR shows an average molecular weight of 994 and approximately 5.3%, by weight, of free catechol. Differential scanning calorimetry shows a Tg of 97° C. To a 1 liter, 3 necked round bottomed flask equipped with a paddle stirrer, condenser thermometer and heating source Complete solution was obtained After the first portion was added the temperature dropped several degrees The temperature of the reaction mixture was raised to 70° C. four more portions were added at 15 minute intervals After five portions were added the temperature of the reaction was raised to 80° C. the remaining three portions were added at 15 minute intervals The reaction product phase separated, with the water layer on top The temperature was then raised to 110° C. The temperature was then raised to 185° C. held for 15 minutes The reaction mixture was held under these conditions for 30 minutes After cooling a dark brown, brittle solid was obtained

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 1 liter, 3 necked round bottomed flask equipped with a paddle stirrer, condenser, thermometer and heating source, were added 135 g (0.80 mole) of 2,6-bis(hydroxymethyl)-4-methylphenol, followed by 9 g (0.10 moles) of oxalic acid and 200 g (1.61 moles) of 4-methylcatechol. To this mixture were added 400 g of water. The reaction mixture was stirred and heated to 70° C. Solution occurred when the temperature reached approximately 60° C. Then, the reaction mixture was heated to reflux and held at reflux for 4 hours. After 1 hour at reflux, the product began to separate. To a 1 liter, 3 necked round bottomed flask equipped with a paddle stirrer, condenser thermometer and heating source reached approximately 60° C Then, the reaction mixture was heated to reflux at reflux for 4 hours After 1 hour at reflux to separate

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A phenolic resin rich in alternating phenolic copolymer block segments was formed by reacting a mixture of 519.0 g of 99 percent pure m-cresol, 538.2 g of 97 percent pure 2,6-bis(hydroxymethyl)-p-cresol and 20 g oxalic acid dihydrate in a solvent mixture of 40 ml deionized water and 200 ml ethyl cellosolve acetate. The reaction mixture was heated to about 70° C. to initiate the reaction forming the alternating copolymer. At 102° C., 32.6 g of 36.9 percent formaldehyde was added in 8 minutes to the reaction mixture to form substantially m-cresol formaldehyde block segments and to chemically bond these segments to the previously formed alternating copolymer. After heating the mixture at reflux for three hours, the amount of heat was increased to remove the water and solvent by distillation. Partial vacuum was applied at about 220° C. and gradually increased to 4 mm Hg to remove the unreacted monomers. Maximum mixture temperature during vacuum stripping was about 226° C. The copolymer was poured from the reaction kettle and allowed to cool. About 840 g of a block copolymer having a number average molecular weight number, Mn, of 1241 Daltons and a Tg of 112° C. were obtained. was formed in a solvent mixture of 40 ml forming the alternating copolymer

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A phenolic resin rich in alternating phenolic copolymer block segments was formed by reacting a mixture of 519.0 g of 99 percent pure m-cresol, 538.2 g of 97 percent pure 2,6-bis(hydroxymethyl)-p-cresol and 20 g oxalic acid dihydrate in a solvent mixture of 40 ml deionized water and 200 ml ethyl cellosolve acetate. The reaction mixture was heated to about 70° C. to initiate the reaction forming the alternating copolymer. At 102° C., 32.6 g of 36.9 percent formaldehyde was added in 8 minutes to the reaction mixture to form substantially m-cresol formaldehyde block segments and to chemically bond these segments to the previously formed alternating copolymer. After heating the mixture at reflux for three hours, the amount of heat was increased to remove the water and solvent by distillation. Partial vacuum was applied at about 220° C. and gradually increased to 4 mm Hg to remove the unreacted monomers. Maximum mixture temperature during vacuum stripping was about 226° C. The copolymer was poured from the reaction kettle and allowed to cool. About 840 g of a block copolymer having a number average molecular weight number, Mn, of 1241 Daltons and a Tg of 112° C. were obtained. was formed in a solvent mixture of 40 ml forming the alternating copolymer

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A phenolic resin rich in alternating phenolic copolymer block segments was formed by reacting a mixture of 519.0 g of 99 percent pure m-cresol, 538.2 g of 97 percent pure 2,6-bis(hydroxymethyl)-p-cresol and 20 g oxalic acid dihydrate in a solvent mixture of 40 ml deionized water and 200 ml ethyl cellosolve acetate. The reaction mixture was heated to about 70° C. to initiate the reaction forming the alternating copolymer. At 102° C., 32.6 g of 36.9 percent formaldehyde was added in 8 minutes to the reaction mixture to form substantially m-cresol formaldehyde block segments and to chemically bond these segments to the previously formed alternating copolymer. After heating the mixture at reflux for three hours, the amount of heat was increased to remove the water and solvent by distillation. Partial vacuum was applied at about 220° C. and gradually increased to 4 mm Hg to remove the unreacted monomers. Maximum mixture temperature during vacuum stripping was about 226° C. The copolymer was poured from the reaction kettle and allowed to cool. About 840 g of a block copolymer having a number average molecular weight number, Mn, of 1241 Daltons and a Tg of 112° C. were obtained. was formed in a solvent mixture of 40 ml forming the alternating copolymer

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A phenolic resin rich in alternating phenolic copolymer block segments was formed by reacting a mixture of 519.0 g of 99 percent pure m-cresol, 538.2 g of 97 percent pure 2,6-bis(hydroxymethyl)-p-cresol and 20 g oxalic acid dihydrate in a solvent mixture of 40 ml deionized water and 200 ml ethyl cellosolve acetate. The reaction mixture was heated to about 70° C. to initiate the reaction forming the alternating copolymer. At 102° C., 32.6 g of 36.9 percent formaldehyde was added in 8 minutes to the reaction mixture to form substantially m-cresol formaldehyde block segments and to chemically bond these segments to the previously formed alternating copolymer. After heating the mixture at reflux for three hours, the amount of heat was increased to remove the water and solvent by distillation. Partial vacuum was applied at about 220° C. and gradually increased to 4 mm Hg to remove the unreacted monomers. Maximum mixture temperature during vacuum stripping was about 226° C. The copolymer was poured from the reaction kettle and allowed to cool. About 840 g of a block copolymer having a number average molecular weight number, Mn, of 1241 Daltons and a Tg of 112° C. were obtained. was formed in a solvent mixture of 40 ml forming the alternating copolymer

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,6-Bis(hydroxymethyl)-p-cresol (30 g, 0.178 moles) (BHMPC), 4-chlororesorcinol (see Table 3), 4-methoxyphenol (see Table 3), and p-toluenesulfonic acid monohydrate (0.8 g, 0.0042 moles) were reacted in 60 ml 2-ethoxyethanol at 90°-95° C. for approximately 4 hours. The solutions were diluted with 250 mL of 2-ethoxyethanol and added dropwise to 2.4 L rapidly stirring H2O. The polymer was collected by filtration, washed 3-4 times with H2O and vacuum dried. See Table 3 for yields. See Tables 1 and 2 for glass transition and alkaline dissolution data. The polymer was collected by filtration washed 3-4 times with H2O and vacuum dried for yields for glass transition and alkaline dissolution data

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,6-Bis(hydroxymethyl)-p-cresol (25.00 g, 0.149 moles), 4-chlororesorcinol (18.26 g, 0.127 moles), 3-methoxyphenol (3.69 g, 0.03 moles) and p-toluenesulfonic acid monohydrate (0.67 g, 0.0035 moles) were reacted four hours and isolated as described in Example 3 (except an additional reslurry/filtration step was added) to yield 40.4 g novolak. See Tables 1 and 2 for glass transition and alkaline dissolution data. The ortho-, ortho-linkages of the alternating copolymers and the terminal groups were identified by 13C NMR analysis. isolated except an additional reslurry/filtration step was added) to yield 40.4 g novolak for glass transition and alkaline dissolution data

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,6-Bis(hydroxymethyl)-p-cresol (25.00 g, 0.149 moles), 4-chlororesorcinol (18.26 g, 0.127 moles), 3-methoxyphenol (3.69 g, 0.03 moles) and p-toluenesulfonic acid monohydrate (0.67 g, 0.0035 moles) were reacted four hours and isolated as described in Example 3 (except an additional reslurry/filtration step was added) to yield 40.4 g novolak. See Tables 1 and 2 for glass transition and alkaline dissolution data. The ortho-, ortho-linkages of the alternating copolymers and the terminal groups were identified by 13C NMR analysis. isolated except an additional reslurry/filtration step was added) to yield 40.4 g novolak for glass transition and alkaline dissolution data

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,6-Bis(hydroxymethyl)-p-cresol (25.00 g, 0.149 moles), 4-chlororesorcinol (13.96 g, 0.09 moles) and p-toluenesulfonic acid monohydrate (0.67 g, 0.0035 moles) were reacted four hours and isolated as described in Synthesis Example 3 to yield 35 g of novolak. See Tables 1 and 2 for glass transition and alkaline dissolution data. The ortho-, ortho-linkages of the alternating copolymers and the terminal groups were identified by 13C NMR analysis. isolated as described in Synthesis Example 3 to yield 35 g of novolak for glass transition and alkaline dissolution data