WO2001046101A9 - Stable bisphenolic compositions - Google Patents
Stable bisphenolic compositionsInfo
- Publication number
- WO2001046101A9 WO2001046101A9 PCT/US2000/034542 US0034542W WO0146101A9 WO 2001046101 A9 WO2001046101 A9 WO 2001046101A9 US 0034542 W US0034542 W US 0034542W WO 0146101 A9 WO0146101 A9 WO 0146101A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bisphenolic
- solvent
- stillbottom
- resin
- water
- Prior art date
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/88—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
Definitions
- This invention relates to a method of manufacturing a stable solution containing bisphenolic stillbottoms.
- This invention also relates to phenolic compositions that are manufactured using solutions of bisphenolic stillbottoms.
- This invention further relates to phenolic compositions that are useful in the manufacture of laminates and paper products.
- Bisphenol A stillbottoms as one example of bisphenolic stillbottoms known in the art, are produced by dehydrocondensing phenol and acetone in the presence of a strong acid catalyst.
- bisphenol A is separated from the reaction mixture by distillation, for example, or by other purification methods, there is a material remaining that has been generally described in the art as a bisphenol stillbottom.
- bisphenol stillbottoms refers to that material separated during the preparation of bisphenol that is not purified bisphenol.
- bisphenol A stillbottoms may contain some bisphenol A.
- the bisphenol A stillbottom typically contains, in predominant proportions, other phenol-acetone reaction products. Dihydroxydiphenylpropane isomers and chromane compounds are typically present in lesser amounts.
- Bisphenolic stillbottoms are a solid at room temperature and typically must be kept in a molten state, or processed into a small particle such as a flake or powder, if the stillbottoms are to be further used in most manufacturing processes.
- Molten stillbottoms are subject to degrading oxidation. Therefore, the chemical composition of the stillbottoms will change as function of the length of storage time in the molten state. As a result of this changing chemical composition, products made using molten stillbottoms may have unpredictable properties.
- the processing of stillbottoms into an intermediate form, such as a flake or powder adds significant cost to products made using this intermediate form and a flake or powder may sinter.
- bisphenolic stillbottoms are incinerated for disposal.
- the use of bisphenolic stillbottoms in phenolic resin compositions has until now been limited.
- the insolubility of bisphenolic stillbottoms generally makes their use prone to problems.
- bisphenol A stillbottoms must be further refined before they are useable in the synthesis of a novolac resin.
- bisphenol A stillbottom are further processed, at extreme temperatures, reduced pressures and in the presence of an alkaline catalyst, to recover phenol and isopropenyl phenol.
- a residue remains after such processing and this residue is said to be useful in the manufacture of novolac resins.
- the water will dissolve inorganic salts and acid impurities, while the phenolic product readily separates from the aqueous solution.
- the development of methods that would allow reuse of bisphenolic stillbottoms have understandably been the object of few prior art attempts.
- One prior art process provides an aqueous suspension of ultrafme bisphenol particles. Strongly alkaline compounds are used in the preparation of such a suspension. This suspension is used in the preparation of polycarbonates.
- Yet another prior art process uses strongly alkaline compounds, such as sodium hydroxide, to provide for the dissolution of bisphenol A in hot water.
- purified bisphenol A may be recovered from a bisphenolic mixture. Fractions of the bisphenolic mixture will dissolve in the hot water in increasing amounts as the amount of sodium hydroxide is increased.
- Purified insoluble bisphenol A is recovered by separation from the liquid portion that contains the soluble fractions.
- Still another prior art process employs a co-solvent, such as an alcohol, to provide for the dissolution of diphenols in water.
- bisphenol A is said to dissolve in a water/alcohol solution that has been heated to reflux. This process is said to be useful in the purification of bisphenol A.
- Each of the prior art processes has disadvantages. A heterogeneous two-phase system of bisphenolic stillbottoms and water is an impractical composition both for the storage of bisphenolic stillbottoms and the use of the stillbottoms in the synthesis of resins.
- the use of strongly alkaline materials or co-solvents adulterates the bisphenolic stillbottoms thus limiting the further use of the modified stillbottoms.
- the use of molten bisphenolic stillbottoms can result in degradation of the bisphenolic stillbottoms thus affecting the properties of resins made using such stillbottoms.
- Preprocessing the bisphenolic stillbottoms into a flake or powder is costly.
- flakes or powders must be re-dissolved during the synthesis of a resin in order for the flake or resin to participate in the synthesis. The re-dissolution presents yet an additional energy requirement.
- Purification of the bisphenolic stillbottoms to another form is an energy intensive process that changes the chemical composition of the bisphenolic stillbottoms, thus further limiting the utility of the modified form.
- the preparation of laminates and resin-impregnated papers using phenolic resins is also known in the art.
- the resins used in such preparations range from low molecular weight resins having a high tolerance for water to high molecular weight resins having a low tolerance for water.
- the present invention provides a stable aqueous solution of bisphenolic stillbottoms.
- the present invention also provides a resole composition that includes in the manufacture of the resin the use of a stable aqueous solution of bisphenolic stillbottoms.
- the present invention further provides a process for using bisphenolic stillbottoms in the synthesis of phenolic resins that does not require refinement of the bisphenolic stillbottom into another chemical form.
- the present invention provides a low molecular weight phenolic resin that exhibits improved paper saturation and reduced phenol emissions during treating when compared to the prior art.
- the present invention also provides a method for making low molecular weight phenolic resins that provide improved paper saturation and reduced phenol emissions during treating when compared to the prior art.
- the present invention further provides a resin, and a method for making such a resin, that results in a paper laminate that can provide improved flexibility when compared to the prior art.
- a single-phase composition of bisphenolic stillbottoms is prepared by mixing water and bisphenolic stillbottoms together under controlled conditions. Surprisingly, it has been determined that when water is mixed with molten bisphenolic stillbottoms, under reflux conditions a stable composition results.
- Such a composition is a single-phase solution at temperatures as low as 75°C, and a single-phase composition that is a semi-solid ranging from a wax-like to a tar-like consistency at room temperature. The single-phase semi-solid can then be reheated to form a single phase liquid.
- the preparation of commercial bisphenolic compounds typically involves a distillation step whereby a purified bisphenolic compound is recovered and a residual bisphenolic stillbottom is separated from the recovered product.
- the bisphenolic stillbottom may also be described as a distillation residue.
- the bisphenolic stillbottom exhibits different chemical properties, including reactivity, as compared to the remainder of the feedstock representing the purified products.
- Bisphenolic stillbottoms useful in the process of the present invention may include bisphenol A stillbottoms. It is generally known in the art that bisphenol A has a purity of at least 98%, on a weight basis and that bisphenol A stillbottoms are of a lesser purity.
- V-390 is a mixture of products produced during the manufacture of bisphenol A.
- V-390 is also known under the synonyms and trade name: BPA tar, BPA isomers, and LE 390 PHENOLIC EXTENDER.
- V-390 has a melting point range of from about 62°C to about 110°C (about 144°F to about 230°F).
- BPA HEAVIES is a mixture of Bisphenol A, o,p-Bisphenol A isomers. and phenol. BPA HEAVIES is also known under the synonyms: 4,4'-Isopropylidenediphenol, and Bisphenol A bottoms. BPA HEAVIES begin to melt at about 62°C (about 144°F).
- Table 1 characterizes a typical bisphenolic stillbottom composition the composition of the present invention.
- the percentages listed in Table 1 are on a weight-per-weight (w/w) basis calculated on the total weight of the bisphenolic stillbottom. It is understood that the component amounts will add up to 100 percent. It should also be evident from the data of table 1, that the bisphenolic stillbottoms of the present invention may contain substantially non- bisphenol A components.
- bisphenol A melts at 150 - 155°C.
- the composition of bisphenolic stillbottoms, as used herein is significantly different from the purified bisphenol product from which the bisphenolic stillbottom is separated.
- the present invention provides a composition that is substantially lower in cost than bisphenol A. Because the composition of the present invention is a stable, single- phase, composition, it is readily used in the synthesis of resins, in place of bisphenol A, as illustrated by the following examples.
- the bisphenolic stillbottoms are first brought to a molten state. This is accomplished in a vessel to which heat may be applied. Once the bisphenolic stillbottoms are in a molten state water is then added to the vessel containing the molten bisphenolic stillbottoms. The weight of water added to the vessel is from about 1% to about 20% based on the combined weight of water and bisphenolic stillbottoms. Because the temperature of the molten bisphenolic stillbottoms may be near or above 100°C, the atmospheric boiling point of water, it is preferred that the vessel containing the molten stillbottoms be so equipped to reflux the water vapor that may evolve from the vessel. The water and the molten bisphenolic stillbottoms are then mixed, for about 30 minutes to about 120 minutes, until a single-phase solution is formed. In a preferred embodiment, the bisphenolic stillbottoms are heated to about
- a typical mixing process is described as follows. Components, including the bisphenolic stillbottoms and water, are introduced into a 1 liter four-necked round- bottom flask. The flask is fitted with means to stir the flask contents, means to monitor the temperature of the flask contents, and means to reflux volatile components and products. Reflux is typically afforded by use of a reflux condenser fitted to one opening of the four-necked flask. The condenser is typically cooled using water. Components are pre-weighed before addition to the four-necked flask. The flask contents are heated by an electric heating mantle that is controlled by a rheostat, or by use of a steam table so that specific temperatures may be reached and maintained. Other arrangements will be known to those skilled in the art.
- Solutions a, c, e, g, and i exhibited homogeneity at both the elevated temperatures (90°C - 100°C ) and at room temperature.
- Solutions b. d, f, and h showed exhibited homogeneity at the elevated temperatures but showed separation into two phases upon standing and cooling to room temperature.
- Cone and Plate Viscosity Determination Aqueous solutions of bisphenolic stillbottoms were tested for viscosity. Viscosity was determined using the well known cone and plate viscosity method.
- the cone and plate viscosity is a high shear viscosity that may be measured on a viscometer such as the Brookfield cone and plate viscometer, model 2000H.
- the Cone and Plate viscometer provides viscosity measurements of small samples utilizing a thermostatically controlled fixed flat plate and a rotating cone. Typically, values measured by the viscometer are converted into centipoise.
- the cone and plate viscosity results reported below were made at a temperature of 75°C.
- the water content of the stable aqueous solutions of the present invention were determined using the standard test method for water by the well known Karl-Fischer titration. This method uses Karl-Fischer reagent which is suitable for determining free water and water of hydration in most solid or liquid organic compositions and for a wide range of concentrations (i.e. from a parts per million order of concentration to pure water). This method is also known under the American Standard for Testing Materials method ASTM E 203-86.
- V-390 PHENOLIC EXTENDER V-390
- the molten V-390 was mixed for 5 minutes. After mixing the molten V-390 for five minutes, water was added to the flask in an amount that was 10%, on a weight basis, of the combined weight of the V-390 and the water. The temperature of the water at the time of addition was nominally 25°C (77°F) and the water was not heated prior to adding it to the flask, although this is not considered a controlling variable. Mixing was maintained during and after the addition of the water. The water immediately began to boil and the temperature of the flask contents rapidly dropped to 100°C (212°F). With mixing, and during the first 20 minutes following the addition of the water, the V-390 and the water maintained separate phases. After about 60 minutes, the temperature of the flask contents had decreased to about 95°C (203°F), under reflux, and the flask contents now appeared clear and homogeneous.
- the now homogeneous solution in the flask was maintained at 95 °C (203 °F) under reflux and mixing for a period of days. Periodically, samples of the homogeneous solution were taken and tests for viscosity, color, and water content were performed on the samples. Table 4 below provides the results of the testing.
- phenolic resins improvements are made in phenolic resins.
- Bisphenolic stillbottoms may be used to produce phenolic resins useful in the making of laminates and resin impregnated papers.
- the stable aqueous solutions of the present invention may also be used in the synthesis of resoles and novolacs. Conventional resole and novolac preparation is further described below and in Phenolic Resins, Chemistry. Applications and Performance, (A. Knop and L.A. Pilato, Springer-Verlag (1985)).
- Resole Synthesis The formation of a resole occurs under generally known conditions. The reaction is carried out at a molar ratio of phenolic compound to aldehyde of 1 :0.2 to about 1 :5. Catalysts typically employed include sodium hydroxide, sodium carbonate, alkaline earth oxides and hydroxides, ammonia, hexamethylenetetramine (“HMTA”) and tertiary amines. Resoles may also form under neutral to mildly acidic conditions. Divalent metal salts, for example, will catalyze resole formation.
- the phenolic compound used in the resole synthesis is preferably phenol itself but may be cresol, xylenols, alkyl substituted phenols, bisphenol A, bisphenol F.
- the aldehyde used in the resole synthesis is preferably formaldehyde but may be another aldehyde such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, benzaldehyde, glyoxal, and furfural.
- the stable aqueous solution of the present invention may also be used in the synthesis of resole derivatives.
- the stable aqueous solution may be used in the synthesis of an alkoxy-modified-resole.
- United States patent no. 4,634,758, herein incorporated by reference in its entirety discloses a process for manufacturing alkoxy- modified resoles.
- the stable aqueous solution of the present invention may be used in the synthesis of a resole modified with an aliphatic polyhydroxy compound. The aliphatic polyhydroxy compound is covalently bound into the resole.
- United States patent no. 5,189,079 herein incorporated by reference in its entirety, discloses a process for making resoles covalently bound with polyhydric alcohols.
- a typical process for resole synthesis is described as follows. Reactants are introduced into a 1 liter four-necked round-bottom flask. The flask is fitted with means to stir the flask contents, means to monitor the temperature of the flask contents, and means to reflux volatile components and products. Reflux is afforded by use of a reflux condenser fitted to one opening of the four-neck flask. The condenser is typically cooled using water. Reactants are pre-weighed before addition to the four-necked flask. The stable aqueous solution of the present invention may be added at any point during the synthesis.
- the weights of reactants are adjusted at the time of addition to account for differences between the nominal assay and the precise assay of the reactant.
- the flask contents are heated by an electric heating mantle that is controlled by a rheostat, or by use of a steam table, so that specific temperatures may be reached and maintained.
- Other arrangements will be known to those skilled in the art.
- larger-scale batches of resoles may also be made.
- the two processes are the same.
- a reactor vessel is used that possesses similar process control capability as the laboratory reaction flask. Therefore, the reactor vessel provides means for mixing reactants, means for measuring and controlling the temperature of the reactants, means for refluxing any volatile compounds in the reactor vessel, and means for distilling off the volatile compounds.
- water tolerance is one means to determine when the bisphenolic stillbottoms are to be added to a partially reacted resole, in order to produce resins that exhibit a preferred paper saturation at an appropriately low free phenol content, as discussed above. If the bisphenolic stillbottom is added at a high water tolerance, the resulting resole has a very slow cure speed. If the bisphenolic stillbottom is added at a low water tolerance, the resulting aqueous resole will not penetrate the paper.
- Novolac Synthesis Novolac resins are obtained by the reaction of a phenol and an aldehyde in a strongly acidic pH region.
- Suitable acid catalysts include the strong mineral acids such as sulfuric acid, phosphoric acid and hydrochloric acid as well as organic acid catalysts such as oxalic acid, para toluenesulfonic acid, and inorganic salts such as zinc acetate, or zinc borate.
- the phenol is preferably phenol itself but a portion of the phenol can be substituted with cresol. xylenols, alkyl substituted phenols such as ethylphenol, propylphenol. and mixtures thereof.
- the aldehyde is preferably formaldehyde but other aldehydes such as acetaldehyde, benzaldehyde, and furfural can also be used to partially or totally replace the formaldehyde.
- the reaction of the aldehyde and phenol is carried out at a molar ratio of 1 mole of the phenol to about 0.40 to 0.85 mole of the aldehyde.
- phenolic novolacs do not harden upon heating but remain soluble and fusible unless a hardener (curing agent) is present.
- the water tolerance test determines the compatibility of the partially reacted resole with water. In this test, the amount of water which may be added to the partially reacted resole while still maintaining a homogeneous solution is determined. The results of the test are expressed in terms of a percentage of the weight of resole equal to the amount of water added.
- the water tolerance test employs distilled or de-ionized water, a laboratory balance, reading to .01 gram, test tubes, a constant temperature bath set to 25°C, and other standard laboratory equipment that will be known to those of skill in the art.
- the distilled or de-ionized water is brought to 25.0 ⁇ 0.1 °C.
- Approximately 10 - 3 grams of a resin sample is weighed into a test tube and the weight recorded.
- 10 - 3 grams of water is added to the test tube.
- the test tube is then capped and shaken to insure that sample is thoroughly mixed with water. If the test tube exhibits a cloud, the test is restarted and a lesser amount of water than first used is added to the test tube.
- test tube is placed in the 25°C water bath and the sample is agitated. Additional water is incrementally added until the cloud point of the sample is reached. The cloud point end point occurs when small white alphanumeric characters on a black background behind the sample can no longer be read when looking through the sample.
- the final total weight of the water added to the test tube is determined and recorded. The water tolerance of the sample is then calculated as the amount of water added to the sample divided by the initial sample weight.
- the unreacted phenol content in phenolic resins may be determined using any of the well known gas chromatographic methods. In the method used in the examples below, a gas chromatograph equipped with an FID detector and a 6' x 1/8" column with 1.2% Atpet-80 and 6.8% di-n-decylphthalate on 60/80 Anachrom ABS is used. The column oven temperature is maintained at about 130°C. the injection port temperature at about 220°C, and the detector temperature at about 220°C. Those of ordinary skill in the art will recognize variations of these components and parameters that may be used. Resin samples are dissolved in a suitable solvent and spiked with p-cresol as a standard. After mixing, the solution of resin, solvent and standard are injected into the gas chromatograph and the areas under the phenol and p-cresol peaks are integrated. The concentration of the free phenol may then be calculated.
- the refractive index of resin samples was determined using the well-known Abbe refractometer. Measurements were made at 25°C, with the prisms of the refractometer maintained at this temperature by a circulating constant temperature bath.
- Resole viscosity was determined using the well-known Brookfield viscometer.
- the Brookfield viscometer measures the viscous resistance to a rotating spindle immersed in a fluid. The torque necessary to rotate the spindle in the fluid is expressed in centipoise.
- a Brookfield Digital Viscometer Model DV-II+ was used. Viscosities were determined at a temperature of 25°C and the Brookfield Viscometer was maintained at about this temperature using a circulating constant temperature bath.
- Gel Time Determination The gel time of a liquid resin is the length of time, typically expressed in minutes, required for a resin to become infusible at a given standard temperature. For this test, a Sunshine Gel Time Meter, catalog number 22, available from Sunshine
- Resole Synthesis - Example 3 To a flask, as described earlier, 100 parts of phenol, 3.5 parts of 50% aqueous 50% sodium hydroxide, 1 part of sodium sulfite, and 14.9 parts of V-390 were added. These components were heated to about 65C, under mixing and atmospheric pressure. Next, 111 parts of aqueous 50% formaldehyde solution was metered into the flask over a 50 minute period. The temperature of these component reactants was held at about 70C and allowed to react under mixing for about 120 minutes. The volatile contents of the flask were then distilled off under vacuum of about 22 inches Hg until a distillate weight of 21.65 Parts was attained.
- the contents of the flask were then held at 65C until a free phenol of about 6.0% was attained.
- the contents of the flask were cooled to 25C and 2.5 parts of acetic acid was added.
- the pH was then adjusted to 6.56 with a small amount of 50% sodium hydroxide.
- the resin thus prepared had a refractive index of 1.5409, a free phenol content of
- the volatile contents of the flask were then distilled off under a vacuum of about 22 inches Hg to a distillate weight of 32.1 parts A residual free formaldehyde content of about 1% was attained.
- the contents of the flask was cooled to about 25°C and 2.75 parts of acetic acid and 6 parts of water was added.
- the resin thus prepared had a refractive index of 1.5405, a free phenol content of 7.8%, and a viscosity of 211 centipoise.
- the gel time of this resin, at 121°C, was 22.9 minutes.
- the temperature was held at 55C for 45 minutes after the addition was completed.
- the contents of the vessel were cooled to about 45C and 2.75 parts of acetic acid was added.
- the pH was then adjusted to 6.86 with acetic acid and the viscosity to 270 cups with water.
- the resin thus prepared had a refractive index of 1.5410, a free phenol content of 5.3%, and a viscosity of 270 cups.
- a resole resin was prepared according to the methods of the present invention using the storage stable solution of example 2. It was discovered that when the storage stable solution was used, no significant difference in resin properties were obtained when compared to a resin prepared using neat bisphenolic stillbottoms.
- the flask contents were then allowed to react under atmospheric pressure at 66°C until a water tolerance of 1030% was obtained. At this point in the reaction the flask contents were cooled to about 60°C. Next, 16.55 parts of the storage stable solution of example 2 was added to the flask. The contents of the flask were then allowed to continue to mix and react for about 10 minutes at a temperature of about 60°C. At the end of the 90 minutes reaction time, the contents of the flask were rapidly cooled to about 25°C, at which point 3 parts of acetic acid was added.
- the resin thus prepared had a refractive index of 1.5402, a free phenol content of 6.0%, and a viscosity of 209 centipoise.
- the gel time of this resin was 22.15 minutes at 121°C.
- Resole Synthesis Using Bisphenolic Stillbottoms - Example 7 To a reactor vessel, as described above, 100 parts of phenol, and 3 parts of a 50% aqueous solution of sodium hydroxide were combined and 1 15 parts of a 50% aqueous formaldehyde solution was then added over a 50 minute period. The contents of the reactor vessel (the "reactants") were heated to about 75°C, under mixing and a vacuum of about 20 inches of Hg, until reflux initiated. The reactants were allowed to react at 75°C under reflux for about 1.5 hours. At the end of this 1.5 hour period, the volatile components of the flask were distilled off at a temperature of about 60°C and a vacuum of about 20 inches of Hg, to a distilled weight of about 22.4 parts.
- the reactants were then held under atmospheric pressure and 65 °C until a water tolerance of 551% was obtained. At this point in the reaction, 8.5 parts of methanol, 15 parts of V- 390, and 2.7 parts of urea were added to the flask. The temperature of the reactor vessel contents was reduced to about 40°C and 1.8 parts of acetic acid were added to the reactor vessel.
- the resin thus prepared was determined to have a refractive index of 1.5373, a viscosity of 191 centipoise, and a free phenol content of 5.3%. The gel time of the resin was 19.1 minutes at 121 °C.
- the volatile contents of the flask were then distilled off under a vacuum of about 25 inches Hg until a distillate weight of 31.9 parts and a residual free formaldehyde content of about 1% was attained.
- the contents of the flask was cooled to about 25°C and 2.75 parts of acetic acid was added.
- the resin thus prepared had a refractive index of 1.5400, a free phenol content of 8.3%, and a viscosity of 175 centipoise.
- the present example demonstrates the manufacture of the resins of the present invention on a large, commercial, scale.
- a reactor vessel as described above.
- 5,963.0 pounds of phenol, and 179.0 pounds of a 50% aqueous solution of sodium hydroxide were combined and 6,858.0 pounds of a 50% aqueous formaldehyde solution was then added over a 50 minute period.
- the contents of the reactor vessel (the "reactants") were heated to about 75°C, under mixing and a vacuum of about 20 inches of Hg, until reflux initiated.
- the reactants were allowed to react under reflux for about 2 hours.
- the temperature of the reactants were held at about 75°C over this 2 hour period.
- the volatile components of the flask were distilled off at a temperature of about 60°C and a vacuum of about 24 inches of Hg to a distillate weight of 1410 pounds.
- the reactants were then held at 70°C under reflux and about 22 inches of Hg until a water tolerance of 393% was obtained.
- the reactor vessel contents were cooled to about 55°C and the vacuum was maintained at about 25 inches of Hg.
- 1151.0 pounds of V-390 was added to the reactor vessel and allowed to mix and react for about 1 hour.
- 161.0 pounds of urea were added to the reactor vessel.
- the temperature of the reactor vessel contents was about 60°C
- the vacuum was about 23 inches of Hg, and the reaction was continued for about 1 additional hour.
- the resin thus prepared was determined to have a refractive index of 1.5435, a viscosity of 271 centipoise, and a free phenol content of 5.0%.
- the gel time of the resin was 18.1 minutes at 121°C.
- the utility of the resins of the present invention may be determined, in part, based on the ability of the resin to penetrate paper.
- One parameter useful in assessing this ability is the amount time it takes the resin to penetrate paper in a standardized test.
- the penetration times reported below were determined using a standardized paper penetration test. This test indicates the capability of the resin being tested to penetrate and completely wet the fibers in a paper sheet.
- the equipment used in the test includes: a pan capable of holding 0.5 to 1.0 inch of the resin and having a minimum diameter of 3.5 inches; a thermometer capable of reading 25.0 + 0.1°C; and a stopwatch.
- the paper used in this test is a Westvaco 1 15 pound basis weight paper. The paper is cut in the shape of a 2 % inch diameter circle. Prior to testing the paper is to be stored in a dessicator containing CaCl 2 • 6H 0 to maintain 31% R.H. (relative humidity) at 24.5°C.
- the resin is brought to a temperature of 25°C.
- the paper disc is placed in the pan of resin with the "shiny" side of the paper facing the liquid resin while simultaneously starting the stopwatch.
- the wetting of fibers is observed as the resin penetration progresses.
- the time when the exposed surface area of the paper disc is initially wet through marks the end of the test. It is this time that is reported as the penetration time.
- the resole of example 6 was made using the storage stable solution of the present invention.
- the resole of example 7 was made using methanol as the solvent. All others are water based products.
- the stable solution of the present invention provides for the manufacture of a resin that allows excellent paper penetration without adversely affecting gel or free phenol content. Furthermore, use of the stable aqueous bisphenolic solution of the present invention allows the manufacture of resin without the addition of methanol, yet exhibiting excellent paper penetration. As seen by the results of table 3, the paper penetration time is very dependent upon when the stillbottoms are added during the resin manufacture.
- the contents of the flask were then further cooled to about 60°C and 10 parts of BPA HEAVIES was added under mixing.
- the contents of the flask was maintained at about 60°C, under mixing, for an additional one hour period. During this one hour hold, 10 parts of water was added to adjust the solids content.
- 2.65 parts of urea was added and the flask contents were cooled to 40°C.
- the flask contents were cooled to 25°C and 1.76 parts of acetic acid was added.
- the resin thus prepared had a refractive index of 1.5390, a free phenol content of
- the resin thus prepared exhibited a gel time of 19.5 minutes at 121°C.
- the contents of the flask were then further cooled to about 60°C and 11.0 parts of a storage stable solution of the present invention, consisting of 90% BPA HEAVIES in aqueous solution, was added under mixing.
- the contents of the flask were maintained at about 55°C, under mixing, for an additional one hour period.
- 2.63 parts of urea was added and the flask contents were cooled to 40°C.
- the flask contents were cooled to 25°C and 1.69 parts of acetic acid was added.
- the resin thus prepared had a refractive index of 1.5396, a free phenol content of 6.4%, and a viscosity of 197 centipoise.
- the resin thus prepared exhibited a gel time of 18.5 minutes at 121°C.
- Example 12 presented below, illustrates novolac synthesis using a bisphenolic stillbottom.
- the resulting product made a novolac of an orange color, tack- free, clear appearance, and having a viscosity of 4880 cps (cone & plate 100 cone; 125C).
- a novolac, thus prepared, is expected to have applications in Abrasives and Friction Industries where higher temperature resistance and less brittleness would contribute to the product maintaining its integrity.
- a comparison of the results of Examples 4 and 8 demonstrates that the use of a bisphenolic stillbottom in the synthesis of a resole resin can result advantageously in a product that has a comparable initial penetration time when compared to a similar resin made using bisphenol A instead of the bisphenolic stillbottom. This also demonstrates a low cost alternative to the use of the alkylidenepolyphenol, bisphenol A.
- the results provided in Table 4 also demonstrate the effect of adding the bisphenolic stillbottom at an effectively infinite water tolerance.
- the water tolerance at the time of addition of the bisphenolic stillbottom is high, because the principle reactants, phenol and formaldehyde, are in aqueous solution and resin solids have not yet been produced.
- the data disclosed herein demonstrates a preferred range of water tolerance at which a bisphenolic stillbottom is added to a reacting resole resin of about 400% to about 1100%. Although it is clear from the examples that the bisphenolic stillbottoms may be added at a water tolerance in excess of 1100%, it is preferred that the residual free phenol be less than the nominally 8% demonstrated in Examples 5, 6 and 9.
- Example 6 employing a storage stable solution of the present invention added at a water tolerance of 1030%, yielded a free phenol concentration of 6%. Accordingly, the preferred upper limit of water tolerance at which a bisphenolic stillbottom is added to the reacting resole resin is about 1100%.
- Reference to Table 5 (example 9) demonstrates that when a bisphenolic stillbottom is added to a reacting resole resin at water tolerance of about 393%, the initial penetration time of the resulting resin is slow. However, when the bisphenolic stillbottom is added at a water tolerance of about 600 - 1000%, the initial penetration time is greatly reduced. Therefore, the preferred lower limit of water tolerance at which a bisphenolic stillbottom is added to the reacting resole is about 400%, as shown by examples 5 and 9.
- the resins of the present invention are useful in, but not limited to, a broad range of laminating and paper preparation processes.
- the resins of the present invention may be used in conventional laminating processes, such as used for the manufacture of kitchen countertops.
- the resins of the present invention may also be used in the preparation of decorative laminates.
- laminate layers are bonded together using a resin.
- the resins of the present invention are thus useful in bonding together the laminate layers.
- the resins of the present invention may be used in the preparation of saturated, or partially saturated, paper products, such as filter paper.
- compositions of the present invention may also be used in paper coatings, or saturating, fiberglass bindings, abrasions, friction composites, particle board, and refractories. Generally, the composition of the present invention may be used where lower emissions and/or plasticity are sought.
- each application of the resins of the present invention may require further modification of the resoles.
- certain laminating processes, or processes used in the preparation of filter paper may require the addition of an alcohol, such as methanol or ethanol, to the resole, to further facilitate paper penetration.
- an alcohol such as methanol or ethanol
- use of the stable aqueous solution of the present invention can eliminate the use of such an alcohol for some applications by virtue of the time at which it is added.
- the effective amount of the resins of the present invention used in the applications in which such resins may be used will vary from application to application. However, such amounts will be readily understood by those of ordinary skill in the art. Furthermore, the methods of making laminates and paper products, as referred to herein, will also be readily understood by those of ordinary skill in the art.
- Embodiments of the present invention also provide laminates made using phenolic resins which exhibit excellent finished product properties.
- Such paper laminates can exhibit reduced emissions during treating when compared to laminates of the prior art because, among other reasons, the elimination of alcohol from the resin formulation and a low free phenol concentration in the resole.
- improved laminates having excellent flexibility may be made according to embodiments of the present invention.
- a storage stable solution of bisphenolic stillbottoms and solvents including water and other solvents is likewise disclosed. It has also been disclosed in embodiments of the present invention resins made using such storage stable solutions. Such resins exhibit a low free phenol content and allow the production of laminates with desirable physical properties related to resin penetration of the paper. Improved laminates having excellent flexibility have also been disclosed in embodiments of the present invention.
- the present invention also provides a method by which paper penetration may be controlled as a function of the water tolerance and the time at which the stillbottoms are added. Other embodiments can be easily envisioned within the basic principles of the present invention.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002392817A CA2392817A1 (en) | 1999-12-22 | 2000-12-19 | Stable bisphenolic compositions |
EP00988170A EP1240124A4 (en) | 1999-12-22 | 2000-12-19 | Stable bisphenolic compositions |
AU24405/01A AU778534B2 (en) | 1999-12-22 | 2000-12-19 | Stable bisphenolic compositions |
US10/070,623 US6716729B2 (en) | 1999-12-22 | 2000-12-19 | Stable bisphenolic compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17135699P | 1999-12-22 | 1999-12-22 | |
US60/171,356 | 1999-12-22 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001046101A1 WO2001046101A1 (en) | 2001-06-28 |
WO2001046101A9 true WO2001046101A9 (en) | 2001-09-20 |
Family
ID=22623443
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/034542 WO2001046101A1 (en) | 1999-12-22 | 2000-12-19 | Stable bisphenolic compositions |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1240124A4 (en) |
AU (1) | AU778534B2 (en) |
CA (1) | CA2392817A1 (en) |
WO (1) | WO2001046101A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2392817A1 (en) * | 1999-12-22 | 2001-06-28 | John George Juras Jr. | Stable bisphenolic compositions |
DE10231851A1 (en) | 2002-07-12 | 2004-01-22 | Bakelite Ag | Polycondensation products, process for their preparation and use |
NL1022425C2 (en) * | 2003-01-17 | 2004-08-03 | Trespa Int Bv | Phenolic resin, use of such a phenolic resin and a molded part produced therewith. |
NL2006218C2 (en) | 2011-02-16 | 2012-08-24 | Trespa Int Bv | A method for reducing the formaldehyde content of a resinous starting material. |
CN114149551B (en) * | 2022-02-09 | 2022-05-13 | 北京玻钢院复合材料有限公司 | Hot-melt phenolic resin, prepreg, composite material and preparation method |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3048508A (en) * | 1958-06-11 | 1962-08-07 | Westinghouse Electric Corp | Resinous compositions and composite laminated members produced therewith |
USRE26881E (en) * | 1969-07-10 | 1970-05-19 | Method of producing an ortho-directed phenolic resin by condensing phenol and hcho in the presence of a bivalent metal ion and then adding resorcinol, and the resultant product | |
GB1467628A (en) * | 1973-04-26 | 1977-03-16 | Shell Int Research | Production of mixtures of bis-hydroxyphenyl-alkanes |
US4124554A (en) * | 1977-02-03 | 1978-11-07 | Union Carbide Corporation | Post-formed aqueous phenolic resin dispersions |
JPS53110922A (en) * | 1977-03-09 | 1978-09-28 | Hitachi Chemical Co Ltd | Resin coated sand for casting |
US4240968A (en) | 1979-04-26 | 1980-12-23 | General Electric Company | Process for isolating and purifying diphenol by-products |
JPS6056729B2 (en) * | 1980-09-29 | 1985-12-11 | アイシン化工株式会社 | Manufacturing method of modified phenolic resin for shell mold |
US4337334A (en) * | 1981-02-10 | 1982-06-29 | Mitsui Toatsu Chemicals Inc. | Process for production of phenolic resin from bisphenol-A by-products |
JPS5874240A (en) * | 1981-10-27 | 1983-05-04 | Aisin Chem Co Ltd | Organic binder for mold |
JPS60261639A (en) * | 1984-06-07 | 1985-12-24 | Dainippon Ink & Chem Inc | Self-curing binder composition for casting mold |
US5552509A (en) | 1992-09-04 | 1996-09-03 | Mitsui Toatsu Chemicals, Inc. | Phenolic resin compositions derived from bisphenol compounds and their condensates |
CA2392817A1 (en) * | 1999-12-22 | 2001-06-28 | John George Juras Jr. | Stable bisphenolic compositions |
-
2000
- 2000-12-19 CA CA002392817A patent/CA2392817A1/en not_active Abandoned
- 2000-12-19 EP EP00988170A patent/EP1240124A4/en not_active Withdrawn
- 2000-12-19 AU AU24405/01A patent/AU778534B2/en not_active Ceased
- 2000-12-19 WO PCT/US2000/034542 patent/WO2001046101A1/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
WO2001046101A1 (en) | 2001-06-28 |
CA2392817A1 (en) | 2001-06-28 |
EP1240124A1 (en) | 2002-09-18 |
EP1240124A4 (en) | 2006-05-10 |
AU778534B2 (en) | 2004-12-09 |
AU2440501A (en) | 2001-07-03 |
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