Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • 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

Definitions

• the present invention relates to a phenol resin composition containing a water-soluble resol type phenol resin and a method for producing the same. More specifically, the present invention relates to a phenolic resin composition having a reduced content of normaldehyde and phenol, and a method for producing such a phenolic resin composition.
• Phenol resin is a typical thermosetting resin used in many fields due to its heat resistance and high mechanical strength. Phenol resins are used, for example, by impregnating or applying them to various base materials, or as binders for various organic and inorganic base materials. Phenol resins are roughly classified into novolak-type phenol resins that are heat-cured by adding a curing agent such as hexamethylenetetramine and resol-type phenol resins that are heat-cured by themselves. It has been.
• phenolic resins hydrophilicity is used in applications that require ammonia-free for environmental friendliness and work environment improvement, and in applications that are used in the form of aqueous solutions or emulsions when solvent-free is required.
• High resole-type phenolic resins are often used.
• the water-soluble resole resin is used, for example, as a binder for abrasive cloth. Resol resin has excellent abrasive grain holding power and heat resistance, and high grindability can be obtained.
• this resol-type phenolic resin contains unreacted phenols and aldehydes, which are undesired substances from the viewpoint of protecting the air environment and the human body environment.
• an excess amount of phenol may be reacted with aldehydes, but a resol-type phenol resin obtained by using an excess amount of phenol. Since it contains a large amount of unreacted phenols, it has poor curability, and the obtained cured product does not satisfy the mechanical strength required by the market. Further, since the resol-type phenol resin obtained by using an excessive amount of phenol with respect to aldehydes contains a large amount of unreacted phenol, it is not preferable to use it from the viewpoint of environment and occupational safety and health.
• Patent Document 1 describes a method for producing a resol resin capable of reducing the amount of unreacted monomers such as formaldehyde and phenol.
• a liquid resin exhibiting a free phenol level of 0.5% or less is produced by blending a phenol-formaldehyde condensate with 0.1 to 0.5 mol of glycine per 1 mol of starting phenol. The method is described.
• Patent Document 1 has room for further improvement in both improving the water solubility of the obtained phenol resin and reducing free formaldehyde and free phenol.
• the present invention has been made in view of the above problems, and the residual amount of both free phenol and free aldehyde, which are unreacted monomers, is greatly reduced, and the resin has high water solubility, so that it is easy to handle or works. It is an object of the present invention to provide a phenol resin composition having excellent properties and a method for producing such a phenol resin composition.
• a phenolic resin composition comprising a water-soluble resole-type phenolic resin and glycine. Phenols and aldehydes, which are starting materials, are reacted in the presence of a basic catalyst under the condition that the molar ratio of [aldehydes] / [phenols] is 0.8 or more and 4.5 or less, and are water-soluble.
• the phenolic resin composition to be used is provided.
• Phenols and aldehydes which are starting materials, are reacted in the presence of a basic catalyst under the condition that the molar ratio of [aldehydes] / [phenols] is 0.8 or more and 4.5 or less, and are water-soluble.
• the process of obtaining a resole-type phenolic resin and A step of adding 0.001 mol% or more and less than 0.1 mol% of glycine to the phenol-type phenol resin as a starting material to obtain a phenol resin composition is included.
• a method for producing a phenolic resin composition is provided.
• the residual amount of both free phenol and free aldehyde is greatly reduced, and the phenol resin composition has high water solubility and is therefore excellent in handleability or workability, and such a phenol resin composition.
• a method for producing a phenolic resin composition is provided.
• the phenolic resin composition of the present embodiment contains a water-soluble resole-type phenolic resin and glycine.
• the phenolic resin composition of the present embodiment is basic with phenols and aldehydes as starting materials under the condition that the molar ratio of [aldehydes] / [phenols] is 0.8 or more and 4.5 or less.
• the process of reacting in the presence of a catalyst to obtain a water-soluble resole-type phenol resin is obtained by a step of adding glycine in an amount of 0.001 mol% or more and less than 0.1 mol% to the phenols as a starting material to this resol type phenol resin.
• the phenol resin composition of the present embodiment contains a water-soluble resol type phenol resin and glycine.
• glycine By containing glycine in the phenol resin composition of the present embodiment, the amount of free aldehyde and free phenol, which are unreacted residual monomers inevitably contained in the water-soluble resol type phenol resin, is reduced. Therefore, the environmental load and the load on the human body are reduced.
• the reason why glycine reduces the amount of free aldehyde and free phenol is not always clear, but the reaction or interaction between glycine and the free aldehyde and free phenol in the phenolic resin composition causes these free aldehydes and It is considered that the free phenol exists as an inert compound.
• the phenol resin composition of the present embodiment contains glycine, so that the stability over time of this phenol resin composition is improved.
• the stability with time of the resin composition means that the change in the characteristics of the resin composition with time is small. Changes in the characteristics of the resin composition over time include increasing the molecular weight of the phenolic resin contained in the resin composition and increasing the viscosity of the resin composition. Since the pH of the phenolic resin composition of the present embodiment is maintained within a predetermined range by the buffering action of glycine, the molecular weight of the resol-type phenolic resin contained in the resin composition can be increased, and unreacted free formaldehydes can be used. Further polymerization reaction with free phenol is inhibited, so that the viscosity of the phenolic resin is increased and the properties of the resin composition are hardly or completely changed.
• the phenol resin composition of the present embodiment contains a water-soluble resol-type phenol resin, and the water-soluble resol-type phenol resin contains phenols and aldehydes as starting materials of [aldehydes] / [phenols]. It is a resol type phenol resin obtained by reacting in the presence of a basic catalyst under the condition that the molar ratio is 0.8 or more and 4.5 or less.
• the resol-type phenol resin produced under the above conditions has high water solubility, and therefore the resin composition containing the resin composition has excellent handleability.
• glycine is used in an amount of 0.001 mol% or more and less than 0.1 mol% with respect to the phenols which are the starting substances used in the production of the resol type phenol resin.
• the phenolic resin composition of the present embodiment has a reduced content of free phenol and free aldehyde even with the use of a small amount of glycine. Therefore, the phenolic resin composition of the present embodiment is inexpensive because the production cost is reduced.
• the phenolic resin composition containing the water-soluble resole-type phenolic resin and glycine of the present embodiment is obtained by the following (step I) and (step II).
• step I Reaction of phenols and aldehydes, which are starting materials, in the presence of a basic catalyst under the condition that the molar ratio of [aldehydes] / [phenols] is 0.8 or more and 4.5 or less. The process of obtaining a water-soluble resole-type phenol resin.
• Step II The reaction mixture containing the resol-type phenol resin obtained in (Step I) is 0.001 mol% or more and less than 0.1 mol% with respect to the phenols as the starting material used in Step I.
• the process of adding an amount of glycine is 0.001 mol% or more and less than 0.1 mol% with respect to the phenols as the starting material used in Step I.
• aldehydes as starting materials used for the synthesis of the water-soluble resol type phenol resin in (Step I) include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, and the like.
• Examples thereof include furfural, glioxal, n-butylaldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, achlorine, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like. These may be used alone or in combination of two or more. It is also possible to use precursors of these aldehydes or solutions of these aldehydes. Above all, it is preferable to use an aqueous formaldehyde solution from the viewpoint of manufacturing cost.
• Examples of the basic catalyst used for synthesizing the water-soluble resole-type phenol resin in (Step I) include hydroxylation of an alkali metal such as sodium hydroxide, potassium hydroxide, or calcium hydroxide, or an alkaline earth metal. Substances; carbonates such as sodium carbonate and calcium carbonate; oxides such as lime; sulfites such as sodium sulfite; phosphates such as sodium phosphate; ammonia, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, Examples thereof include amines such as hexamethylenetetramine and pyridine.
• an alkali metal such as sodium hydroxide, potassium hydroxide, or calcium hydroxide, or an alkaline earth metal.
• carbonates such as sodium carbonate and calcium carbonate
• oxides such as lime
• sulfites such as sodium sulfite
• phosphates such as sodium phosphate
• ammonia trimethylamine, triethy
• the compounding molar ratio (F / P) of the phenols (P) and the aldehydes (F) is 0.8 or more, preferably 0.8 or more and 4.5 or less, more preferably.
• the reaction is charged at a ratio of 0.9 or more and 3.0 or less, more preferably 1.0 or more and 2.8 or less, and even more preferably 1.2 or more and 2.5 or less, and further polymerized. It is carried out by adding the above-mentioned basic catalyst as a polymerization catalyst and performing reflux for an appropriate time (for example, 3 to 6 hours).
• the compounding molar ratio (F / P) of the phenols (P) and the aldehydes (F) is less than 0.8, the weight average molecular weight of the water-soluble resol-type phenol resin produced is small, which is desired. It may not have properties such as heat resistance.
• the compounding molar ratio (F / P) of the phenols (P) and the aldehydes (F) exceeds 4.5, the gelation of the resin is likely to proceed during the reaction, and the reaction efficiency is lowered. However, it is not preferable because a water-insoluble high molecular weight resol-type phenolic resin is produced.
• the reaction temperature is, for example, 40 ° C to 120 ° C, preferably 60 ° C to 100 ° C.
• the weight average molecular weight of the water-soluble resole-type phenol resin is preferably 250 to 3000, and more preferably 300 to 2000.
• the resol-type phenol resin having a molecular weight in the above range has water solubility and is excellent in handleability.
• the basic catalyst used in (Step 1) is, for example, in an amount of 1 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 5% by weight, based on the phenols as the starting material. Used in.
• a basic catalyst in an amount in the above range, the reaction efficiency between phenols and aldehydes can be improved, and thus the amount of phenols and aldehydes remaining as unreacted substances can be reduced.
• Step II (Step II) is followed by (Step II).
• (Step II) 0.001 mol% or more and 0.1 mol of the reaction mixture containing the resol-type phenol resin obtained in (Step I) was added to the phenols as the starting material used in (Step I). Less than% of glycine is added.
• the amount of glycine added is preferably 0.001 mol% or more and 0.098% or less, more preferably 0.001 mol% or more, based on the phenols of the starting material used in (Step I). It is 0.095 mol% or less.
• Step II it is preferable to gradually add glycine to the reaction mixture obtained in (Step I) in predetermined amounts over a predetermined time.
• the addition of glycine is carried out at a temperature of 60 ° C. to 75 ° C., preferably at a temperature of 60 ° C. to 65 ° C., in an amount of 0.5 to 20% by mass, preferably 1 to 10% by mass, based on the total amount of glycine per minute. %, More preferably 2.8% by mass to 4% by mass.
• glycine may be used in the form of an aqueous solution.
• glycine may be used in the form of a metal salt such as a sodium salt.
• the phenol resin composition of the present embodiment is obtained by slowly cooling the temperature of the reaction mixture to about room temperature.
• the phenolic resin composition obtained through the above steps has an unreacted free phenol content of 5% by mass or less, preferably 2% by mass or less, more preferably 2% by mass or less, based on the entire phenolic resin composition. It is reduced to 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.6% by mass or less.
• the phenol resin composition obtained by using the above steps has an unreacted free aldehyde content of 5% by mass or less, preferably 2% by mass or less, more preferably, with respect to the entire phenol resin composition. Is reduced to 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.6% by mass or less.
• the pH of the phenolic resin composition obtained by using the above steps is close to neutral, for example, 5 to 10, preferably 6 to 8, and more preferably 6.5 to 7.8. Yes, and even more preferably, it is 6.8 to 7.5. Such pH is achieved by the presence of glycine in the resin composition.
• the phenolic resin composition of the present embodiment is excellent in stability over time by having a pH in the above range.
• Viscosity increase rate (%) [(Viscosity after storage) / (Viscosity before storage)] ⁇ 100 The smaller the value of the viscosity increase rate, the better the stability over time.
• the resulting reaction mixture (resin composition) was transparent, had a solid content of 55%, had a pH of 7.4, and had a dilution in water greater than 2000% at 20 ° C.
• the amount of unreacted phenol measured by gas chromatography was 0.25% by mass, and the amount of unreacted formaldehyde was below the detection limit (0.1% by mass).
• the change in viscosity of this resin composition over time was measured in the same manner as in the method described in Example 1, and the change over time was evaluated. The results are shown in Table 1.
• reaction mixture (resin composition) was transparent, had a solid content of 54.8% by weight, had a pH of 7.4, and had a dilution in water greater than 2000% at 20 ° C. ..
• the phenolic resin composition of the example was excellent in handleability because the residual amount of unreacted phenol and unreacted aldehyde was reduced and the change in viscosity before and after storage was reduced.

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• Chemical Kinetics & Catalysis (AREA)
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• Organic Chemistry (AREA)
• Phenolic Resins Or Amino Resins (AREA)

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• 2021
  • 2021-10-13 EP EP21897527.4A patent/EP4253441A4/en active Pending
  • 2021-10-13 CN CN202180079669.2A patent/CN116457382A/zh active Pending
  • 2021-10-13 US US18/036,021 patent/US20250075022A1/en active Pending
  • 2021-10-13 JP JP2022515709A patent/JP7180815B2/ja active Active
  • 2021-10-13 WO PCT/JP2021/037861 patent/WO2022113549A1/ja not_active Ceased
• 2022
  • 2022-06-10 JP JP2022094177A patent/JP2022111350A/ja active Pending

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