DE2635132A1 - PROCESS FOR MANUFACTURING PHENOLIC RESIN AND PHENOL-FORMALDEHYDE MATERIAL - Google Patents

Description

28 317 n / wa

MATSUSHITA ELECTRIC WORKS, LTD. KADOMA-SHI

JAPAN

Process for the production of phenolic resin and phenol-formaldehyde material

The invention relates to a phenol-formaldehyde material. The invention particularly relates to a material that Phenols and formaldehyde, which is used to make phenolic resins, which is obtained by being

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Formaldehyde dissolves in phenols and absorbed.

So far, materials comprising phenols and formaldehyde have not become known and therefore are natural no uses for such materials have been considered.

As examples of conventional materials that contain formaldehyde, 37% formaldehyde (formalin), highly concentrated Formalin, solid paraformaldehyde and the like can be cited.

Formalin contains 37% formaldehyde, about 8 to 10% by weight methanol and the remainder water. When the focus is on Formaldehyde is low or the methanol content is high, the reaction rate with phenols is poor, whereby a long period of time is required for the reaction. In addition, assume about 63% by weight of water and methanol do not participate in the reaction and will necessarily be removed later.

Highly concentrated formalin contains 43 to 47% by weight of CH ₂ O, the CH 1 O concentration being greater than that of the formalin listed above. However, in order to prevent precipitation, methanol is further added so that the amount of methanol becomes 43 to 50% by weight. As a result, the reaction with phenols is further slowed down, thereby increasing the reaction time without any benefit.

Paraformaldehyde is a solid material that more

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Contains more than 80% by weight of CH 4 O and less than 1% by weight of methanol and in order to obtain this, an aqueous formaldehyde solution must be subjected to a dehydration treatment will. Since such dehydration is carried out at high temperatures, the molecular weight decreases therefore, it takes extended periods of time to mix and dissolve it with phenols. on the other hand Since the reaction speed is high, the reaction system becomes heterogeneous, thereby obtaining a gelled resin can be. In addition, charging with paraformaldehyde is disadvantageous in reactions because it is not is in the form of a liquid.

Furthermore, so far in the production of phenolic resins (e.g. resols or novolaks) are phenols and a 37% strength aqueous solution of formaldehyde (formalin) mixed, heated and reacted in the presence of a catalyst, the resins thereby obtained having been dehydrated. However, such methods have the following disadvantages on:

(1) As the concentration of a phenol-formaldehyde reaction system is low, the conversion is also low, which is why this results in a considerable amount of unreacted Material remains. For this reason, the resins obtained are not yet complete in their properties satisfactory such as in their heat resistance or curing speed.

(2) When dehydrating, a significant amount of water must be removed, with the product effectiveness

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is low. In addition, the salary of the unimplemented Controlled materials in the dehydration stage.

(3) In the case of the transport of raw materials to the factory, phenols and formaldehyde must be separated and individually be transported. In the case of formalin, it is also disadvantageous from an economic point of view because formalin is formed in the form of an aqueous solution and then transported, reacted and dehydrated will.

In order to overcome the disadvantages associated with dehydration in conventional techniques, the direct one Reaction of phenols and formaldehyde polymers has been attempted. In such a case, however, the formaldehyde polymers dissolve does not easily occur in phenols. However, if you try to dissolve them by heating, the thermal heat of decomposition and the heat of dissolution of formaldehyde and the heat of reaction of phenols with formaldehyde released at the same time, making it difficult to control the reaction temperature and gelling the resins will. In addition, the properties of the resins obtained are poor, since a considerable amount of gas is generated during curing occurs, heat resistance is poor, removal from the mold when deforming cannot be performed well be, etc.

In addition, conventional resoles are insoluble in water and are used in the form of a varnish, which in

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organic solvents such as methanol, ethanol, benzene, toluene and xylene. The organic solvents however, are generally flammable and sometimes toxic. Therefore, various disadvantages arise.

So far, water-soluble resols are produced by the reaction of phenol and formalin in a highly alkaline environment (around pH 11) using caustic soda. However, due to the residue remaining in the resin Catalyst properties such as insulation resistance after boiling in water are very poor, hence it cannot be used as a resin for laminated panels and only as an adhesive for plywood finds.

Moreover, in the case of producing a resin for laminated panels, formalin is generally used within of the pH range of 8 to 10 is used, but in such a case a significant amount of water in the Reaction system exists, whereby the formaldehyde concentration in the reaction system low and the methylolation reaction get slow. Therefore, to increase the conversion of formaldehyde above 65% (if this is below 65% the unreacted materials increase and the Yield is poor) a long reaction time is required and since the methylation reaction proceeds in this time, the resols obtained have a broad molecular weight distribution, i.e. have a considerable one Amount of methylolated, polynuclear compounds. Therefore are resoles, which are low compared to water

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Affinity, i.e. having poor water miscibility, is hardly maintained and it is difficult to dissolve in water to train.

For this reason, in the case of using resols for laminated panels as varnish, in which this only uses water to adjust their viscosity are diluted, the paints become cloudy, which is why uniform paints or varnishes are not available. the end for this reason, the use of organic solvents such as methanol is inevitable. Organic solvents will be removed during evaporation in a drying stage after an immersion stage, but this is out of sight the cost of the print treatment and the like are not preferable. In addition, there is the drying stage Risk of explosion.

Thus, provided the resol could be solubilized with water It would be expected that paints using water as a solvent would become available, without the need for expensive solvents to use, whereby there would be no risk of explosion and the production capacity could be increased using increased drying temperatures.

On the other hand, increasing the reaction rate using paraformaldehyde is one purity more than 80% have been considered. In such a case, there is methylolation in the reaction in the presence of an alkali catalyst (pH above 8.0)

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goes very violently, impossible to produce stable resols, since the control of the reaction temperature it is difficult to have side reactions or deflagrations or gelations are caused.

The invention overcomes the disadvantages set out above and provides a material useful as a raw material for producing phenol-formaldehyde resins is.

If the inventive material for the production of When using phenolic resins, the following properties can be obtained:

(1) The transportation cost of the raw materials is extreme small amount.

(2) The material can immediately after a reaction the addition of a suitable catalyst with or without controlling the component ratio of Phenols and formaldehyde in the material are subjected.

(3) When the material is subjected to a reaction, the reaction control is easy and the conversion is high .

(4) Post-reaction dehydration is unnecessary or easy to perform when necessary, and therefore this kept production costs low

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can be. In addition, the response time is short.

(5) The material has excellent storability.

The invention is therefore based on the object of creating a material that comprises phenols and formaldehyde, which is suitable for the production of phenolic resins.

The above object of the invention is achieved by providing a material which essentially from one or more phenols and from about 0.5 to about 5 moles, per 1 mole of the phenol or phenols, formaldehyde consists.

The invention also provides a process for the production of phenolic resins, which the reaction one or more phenols with 37% formaldehyde in the presence of a catalyst, the reactants are available from a material that contains one or more phenols and no more than 6 moles of formaldehyde per liter Moles of the one or more phenols, which is formed by dissolving formaldehyde in one or more phenols is produced.

The phenols which form the material according to the invention, are not particularly limited and any one or more phenols (hereinafter often only to

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"Phenols" for short) which can be used as the raw material for phenolic resins which are produced by reacting with formaldehyde can be used. Examples of the phenols include phenol, cresols, xylenol, alkylphenols, such as ethylphenol, propylphenol, hexylphenol, nonylphenol or cashew nut shell liquid, alkenylphenol, such as Isopropenyl phenol, polyhydric phenols such as resorcinol, or the like. Among these are Phenols having a melting point of not more than about 50 ° C in view of the subsequent treatment of absorption of formaldehyde, preferred. With regard to the purity of the phenols, there is no restriction as long as when there are no problems in the production of the phenolic resins. The phenols can be any desired solvent contain. The phenols can be used individually or in mixtures.

The formaldehyde used in the invention can be in the form of a gas, a liquid or a mixture thereof can be used, the gaseous form being preferred. There was also the use of paraformaldehyde etc. in Considered, which, however, does not meet the features of the invention.

Formaldehyde is generally produced by thermal decomposition of paraformaldehyde, air oxidation of methanol, dehydrogenation from methanol, thermal decomposition of hemi-acetal, or the like. With regard to the manufacturing methods there are no restrictions on formaldehyde, and formaldehyde obtained in any way can be used according to the invention Find application. Generally exist in terms of

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There are no restrictions on the purity of the formaldehyde, provided that there are no Difficulties arise. The formaldehyde can contain gases such as oxygen, nitrogen, hydrogen, carbon dioxide, carbon monoxide, etc. as impurities, diluent gases or included with regard to other purposes.

In general, although the invention is not limited thereto, the material of the invention is carried out by Production of phenols in a liquid state, introduction of formaldehyde and its absorption and dissolution manufactured herein. In principle, there are no restrictions on the manner in which the device, the conditions etc. applicable to the above Operations are applied. The main object of the invention is to provide a material that phenols and Includes formaldehyde, and as long as such a material can be obtained, persist in terms of its manufacture no restrictions.

A preferred embodiment will now be described the introduction of formaldehyde into phenols.

The phenols are produced in liquid form and kept at a suitable temperature. Then it becomes formaldehyde introduced into the phenols for absorption and dissolution. In the case of absorption and dissolution of formaldehyde the preferred temperature of the phenols is from about 40 to about 100.degree. C., although it is desirable to be in the range of low temperature side to work to such an extent that no polymerization of formaldehyde or

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Solidification of the phenols is effected. In such a material the formaldehyde is in an amount of no more than about 6 moles, preferably 0.5 to 5 moles, more preferably 0.5 to 3 moles, per 1 mole of the phenols before.

The pressure of absorption (or dissolution) can vary widely, but is typically atmospheric is being worked on. The general rule in this regard is that there are no significant benefits when applied sub-atmospheric pressures are available for absorption and, in fact, absorption times are increased, therefore, the rate of absorption is often increased by operating at superatmospheric pressures can. In general, however, those required for operation at superatmospheric pressures can be complicated Make apparatus uneconomical to work with superatmospheric pressures.

The material according to the invention can be water or water and methanol as optional components. The reason for the presence of such components lies in maintaining a good shelf life of the material. Specifically the simultaneous presence of water and methanol gives excellent storage stability. . For example, the material composed of phenols and formaldehyde becomes cloudy at room temperature, although the turbidity can be removed by heating the material to, for example, above about 50.degree. A material that from phenols, formaldehyde and water or water and

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Methanol is made, but it is a transparent liquid even at room temperature.

A material that includes phenols, formaldehyde, and water, can be obtained in the same manner as mentioned above. In such a case, water can (which is a component of the material) can be mixed with phenols or in formaldehyde at the same time or to which are added by absorption and dissolution of the formaldehyde in the phenols *. The most preferred Way consists in the use of a mixture of formaldehyde and water, which in the case of oxidation of methanol using excess air (cf. "The Oxide Catalyst Process", G.F. Walker "Formaldehyde", P. 9, 19 64) for obtaining formaldehyde, and its absorption and dissolution in phenols. It is preferred that the water in such material be in an amount no greater than about 7% Moles, with 0.05 to 4 moles being more preferred, are present per 1 mole of phenols.

The material including phenols, formaldehyde, water and methanol can also be obtained in the same manner as this has been described above. In such a case, methanol and water can previously be converted into phenols or formaldehyde may be mixed or one produced by absorption and dissolution of formaldehyde in phenols Material can be added. It is preferred that in such a material water in an amount of not greater than about 7 moles, more preferably from 0.05 to 4 moles, is present per 1 mole of phenols, and that the methanol

* included material

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is present in an amount of no more than about 7 moles, more preferably 0.05 to 4 moles, per 1 mole of phenols.

In view of the task according to the invention, the use of a mixture of formaldehyde and water is and methanol obtained by dehydration using insufficient air access is, most preferred (see "The Silver Catalyst Process", G.F. Walker "Formaldehyde", p. 21, 1964). A Such a mixture, which is soluble in phenols, generally contains 40 to 80% by weight of formaldehyde, 10 to 30% by weight Water and 10 to 30% by weight of methanol, even if such a mixture is absorbed directly and in phenols is dissolved, the desired material according to the invention can be easily obtained.

To control the amount of water and methanol in the material, the following methodologies can be used will:

(1) A material obtained by absorbing and dissolving formaldehyde, water and methanol in phenols is subjected to distillation. In such an operation, methanol removal is or are and / or dehydration to obtain a material which has the desired components, carried out. Distillation is not limited to any specific methodology and distillation at reduced pressure, pressure distillation, distillation

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at normal pressure, refining, etc., can be used will. However, the reduced pressure distillation, the normal pressure distillation and the Refining most preferred. With such distillations it is impossible to get all of the methanol to remove. It is believed that this is due to the fact that in the material (Solution) Hemi-acetal is formed. With a view to increasing the storage stability of the material the simultaneous presence of methanol in a suitable amount is quite preferred.

(2) A mixture (40 to 80% by weight formaldehyde; 10 to

30% by weight of water; 10 to 30% by weight of methanol) by dehydration using an insufficient Amount of air has been obtained is condensed, for example by absorption in water, and then a distillation as mentioned in (1) above to obtain a material of 50 to 80% by weight of formaldehyde, not more than 3% by weight of methanol, the remainder being water or other impurities. The resulting material is made to obtain a material that has the desired component ranges has, absorbed and dissolved in phenols.

In any case, it is preferable that the material obtained by the above methodology (1) or (2) has the following composition: Not more than about 6 moles, preferably 0.5 to 5 moles, even more preferably 0.5 to 3 moles of formaldehyde, no more than about

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7 moles, preferably 0/05 to 4 moles of water, and not more than 7 moles, preferably 0.05 to 4 moles, of methanol per 1 mole of phenols.

The material containing formaldehyde and phenols and optionally water or water and methanol can be in any can be prepared in any conventional manner, although it is preferred to use the methodology of introducing a Mixture containing formaldehyde obtained by air oxidation of methanol to be used in phenols.

Phenolic resins including resols and novolaks, can be made from the materials according to the invention in the same way as in the conventional one Reaction of phenols and formalin, i.e. by reacting the materials in the presence of a suitable catalyst, getting produced. The above-mentioned materials are particularly useful as raw materials for Production of phenolic resins and epoxy resins of the bisphenol type suitable.

If the formaldehyde / phenol molar ratio is less than 0.5, there is no crosslinking density during the curing stage, which is why curing is not carried out completely can be, while in contrast, if the formaldehyde / phenol molar ratio exceeds 5, a Gelation can occur. A formaldehyde / phenol molar ratio within the range of 0.5 to 3 is preferred, to completely rule out gelation. Furthermore

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is, if the amount of further components is less than their lower limit, the equilibrium of the methylolation reaction and the rate of methylation is disturbed, the desired phenolic resins not being available are. However, if the upper limit is exceeded, the reaction takes place only slowly because the methanol acts as a response retarder, reducing response times get long.

With regard to the reaction conditions for formation of such phenolic resins, it is preferred, this is not limitative to carry out the reaction at temperatures of 70 to 11O ⁰ C. If the reaction temperature is lower than 70 ° C, the reaction proceeds too slowly, which is impractical, while if the reaction temperature is over 110 ° C, the reaction proceeds too vigorously. The reaction time is generally 60 to 300 hours, although it varies depending on the charging conditions. The reaction is conveniently carried out at atmospheric pressure, although sub- or super-atmospheric pressures can also be used if desired.

Any acidic, neutral or alkaline catalyst can be used as the reaction catalyst has found widespread and conventional use in the manufacture of phenolic resins. Examples of acidic catalysts include hydrochloric acid, sulfuric acid, oxalic acid, Phosphoric acid, p-toluenesulfonic acid, or the like. Examples of neutral catalysts include zinc acetate,

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Manganese acetate or the like. Examples of alkaline catalysts include caustic alkali (e.g. caustic soda, caustic potash), sodium carbonate, organic Amines or the like.

The pH of the reaction depends on the type of catalyst used and in the case of using one neutral or acidic catalyst, the reaction is carried out at a pH of 1 to 6, while in the case of the The reaction is carried out at a pH of 7.5 to 11 using a neutral or basic catalyst will. The catalyst is used in such an amount that the pH of the reaction system is in the desired Area lies.

As is conventionally known, there is a close relationship between the formaldehyde / phenol molar ratio the starting material, the type of catalyst used (i.e. the pH range) and the type of ultimately obtained resin. The same fact applies to the production of the phenolic resins using the starting material according to the invention. So, in the case of carrying out the reaction with a material that is a Formaldehyde / phenol molar ratio of not more than 1 in the presence of neutral or alkaline catalysts obtained at a pH of 7.5 to 11 resoles (viscous liquid). On the other hand, in the case of Carrying out the reaction with a material that is a Formaldehyde / phenol molar ratio of no less than 1, in the presence of a neutral or acidic

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Catalysts at a pH of 1 to 6 novolaks (fixed) received.

Further, in the case of producing water-soluble resoles using the material according to the invention, which is an important feature of the invention, the reaction in the presence of calcium hydroxide and / or barium hydroxide carried out at a pH of 7.5 to 9, preferably 8.0 to 8.5. Laminates made using the resulting water-soluble resols produced and thereby obtained, show excellent water resistance, especially resistance to boiling water.

Before it is subjected to the reaction, the material comprising formaldehyde and phenol can be used for the production of phenolic resins according to the invention is used, with water to regulate the formaldehyde / phenol ratio can be diluted to an appropriate and desired ratio.

Further, after the reaction, it can be neutralized with an acid or with a base in a conventional manner.

In addition, after the neutralization, desalination can be carried out in a known manner.

The one using the material according to the invention The phenolic resins obtained can be used on a wide scale, for example, as a varnish for the production of laminated panels,

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can be used as an adhesive for plywood, materials for deformation, or the like.

The invention is further illustrated by the following examples, which, however, are not to be construed as limiting are.

Production example 1

100 ml of liquid paraffin was introduced into a 2-liter three-necked flask, and nitrogen gas was passed therethrough at a supply rate of 0.5 / min while heating at 150 to 180 ° C. A mixture of 90 g of paraformaldehyde powder and 150 g of liquid paraffin was gradually added dropwise to the flask over 45 minutes. The gas generated therein was fed into a 200 ml flask in which 94 g of phenol at 95 ° C. was filled, and was absorbed therein for 60 minutes. The achieved weight increase of the material was 22 g and as a result of the CH ₂ O analysis by the hydrochloric acid-hydroxylamine method, the molar ratio of formaldehyde / phenol was 0.7.

The obtained material was left to stand for 7 days at room temperature. The material remained homogeneous and no change was observed _{with regard to the CH 2 O component.}

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Production example 2

Formaldehyde gas generated in the same manner as in Example 1 was fed into a 200 ml flask in which 94 g of phenol at 95 ° C. was filled and absorbed therein for 150 minutes. No specific violent heat absorption or generation was observed during the absorption. The increase in weight of the material obtained was 61 g and as a result of the CH ₂ O analysis, which was carried out as in Example 1, the molar ratio of formaldehyde / phenol was found to be 2.0.

The material obtained was a homogeneous solution at temperatures above 35 ° C. and turned white at temperatures below which, however, when heated to ubi
sung revealed.

Temperatures above 35 C and discolored below 35 ° C

a uniform, transparent solution at over 50 C

In addition, the material was kept at room temperature for 7 days left to stand, with no change in the components being found.

Production example 3

100 ml of liquid paraffin was placed in a 2 liter three-necked flask and nitrogen gas was passed therethrough with heating at 150 to 180 ° C at a feed rate of 0.5 l / min. A mixture of 100 g of paraformaldehyde powder and 60 g of water

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then gradually became the flask over 120 minutes added drop by drop. The gas generated herein was taken into a 200 ml flask containing 94 g of phenol at 95 ° C contained and was absorbed over 160 minutes.

The resulting material contained 3.01 moles of formaldehyde and 3.3 moles of water per 1 mole of phenol.

The material was left to stand for 3 days at room temperature and maintained its homogeneity; no change in the components was found.

Production example 4

A material was obtained in the same manner as in Example 3, with the exception that a mixture of 100 g paraformaldehyde and 30 g water were used and the absorption was carried out for 170 minutes,

The material obtained contained 2.5 moles of formaldehyde and 1.6 moles of water per 1 mole of phenol.

The material was left to stand for more than 2 days, it maintained its stability, and it became no change in the components found.

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Production example 5

Formaldehyde gas was generated in the same manner as in Example 3, and water vapor was mixed therewith to obtain a mixed gas of 80% by weight of CH ₉ O and 20% by weight of H ₉ O. The mixed gas was introduced into phenol for 170 minutes and absorbed and dissolved in the same manner as in Production Example 3.

The material obtained contained 4.5 moles of formaldehyde and 1.88 moles of water per 1 mole of phenol.

The material was stable for one night and one day and no change in the components was observed.

Production example 6

In a tubular reactor (diameter 55 mm) were introduced: 1.2 kg / h of methanol and 12.4 m ³ / h of air (air / methanol ratio (l / g) = 10.3) and the reaction was carried out at 35O ° C in the presence of 40 g of MoO _ catalyst while obtaining a mixed gas of formaldehyde and water (62.5% by weight CH ₃ O and 37.5% by weight H ₃ O).

The resulting mixed gas was introduced into 94 g of phenol placed in a 200 ml flask (at 95 ° C) and was absorbed therein for 170 minutes. While

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no specific rapid heat absorption or generation was observed after absorption.

The material obtained contained 2.5 moles of formaldehyde and 2.5 moles of water per 1 mole of phenol.

The material was left at room temperature for more than a week left to stand, but no change occurred. In addition, after it was during 3 days was left to stand at room temperature, no change in the components was found.

Production example 7

A material was obtained in the same manner as in Production Example 3 except that a Mixture of 110 g of paraformaldehyde powder, 44 g of water and 22 g of methanol was gradually added dropwise thereto. The weight gain of the obtained material was 158g and it was made as a result of the CHjO analysis confirms the hydrochloric acid hydroxylamine methodology, that 3.28 moles of formaldehyde, 0.69 moles of water and 2.1 moles of methanol were present per 1 mole of phenol.

The obtained material was allowed to stand at room temperature for more than 4 days and none occurred White discoloration and solidification. In addition, no change in the components was found will.

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Production example 8

A material was obtained in the same manner as in Production Example 7 except that 26 g Water were used. The weight gain of the material obtained was 170 g. The material was 3.5 moles Formaldehyde, 1.17 moles of water and 1.38 moles of methanol per 1 mole of phenol.

The obtained material was left to stand for 3 days at room temperature, maintaining its stability and no change in the components was found.

Production example 9

5.0 kg / h of methanol and 4.43 m ³ / h of air (air / methanol ratio (l / g) = 0.88) were introduced ^{into a tubular reactor (diameter 35 mm) and the reaction was carried out at 601 °} C. in the presence of a cylindrical silver network catalyst (diameter of the silver wire: 0.22 mm; diameter of the cylinder: 0.5 mm; length of the cylinder: 150 mm) to obtain a liquid with 53% by weight of formaldehyde, 37% by weight of water and 10% by weight .% Methanol carried out. The obtained liquid was condensed to obtain a liquid containing 80% by weight of formaldehyde, 10% by weight of water and 10% by weight of methanol. The resulting liquid was mixed with phenol heated at 50 ° C to obtain a material

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mixed, the 5.5 moles of formaldehyde, 1.11 moles of water and Contained 0.73 moles of methanol per 1 mole of phenol.

The material was allowed to stand at room temperature for more than 10 hours; it kept its stability upright and no change in the components could be observed.

Production example 10

The liquid obtained in Production Example 9 was mixed with phenol heated at 50 ° C. to obtain a material mixed, the 1 mole of phenol, 5.5 moles of formaldehyde, 1.11 moles Contained water and 0.63 mol of methanol.

500 g of the obtained material (solution) were at a temperature of 50 to 52 ° C under a pressure of 200 mmHg Distilled for 27 minutes with elimination of 34 g of a 55% strength by weight aqueous methanol solution. The material after distillation contained 5.5 mol of formaldehyde, 0.6 mol of water and 0.28 mol of methanol per 1 mol of phenol.

Preparation example 11

300 g of the solution obtained in Preparation Example 10 were heated at 103 ° C. at atmospheric pressure for 67 minutes distilled to eliminate 14.2 g of a 55% by weight aqueous methanol solution. The material contained after

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of distillation, 5.5 moles of formaldehyde, 0.77

Moles of water and 0.38 moles of methanol per 1 mole of phenol.

Production example 1 2

In the same tubular reactor used in Preparation Example 9, 5.0 kg / h of methanol and 1.35 in ³ / h of air (air / methanol ratio (/ g) = 0.26) were introduced, and the reaction was carried out carried out at 420 ° C. in the presence of the same catalyst as that used in Preparation Example 9, a liquid being obtained which had 49% by weight of formaldehyde, 12% by weight of methanol and 39% by weight of water. The obtained liquid was condensed to obtain a liquid containing 70% by weight of formaldehyde, 10% by weight of water and 20% by weight of methanol. The liquid was mixed with m-cresol heated to 55 ° C to obtain a material containing 4.0 moles of formaldehyde, 0.55 moles of water and 1.05 moles of methanol per 1 mole of m-cresol.

237 g of the material (solution) were at 52 to 57 C at 200 mmHg for 30 minutes with the elimination of 19 g a 55% by weight aqueous methanol solution is distilled. After distillation, the material contained 4.0 moles of formaldehyde, 0.05 moles of water and 0.7 to 2 moles of methanol per 1 mole of m-cresol.

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Production example 13

500 g of the liquid (before condensation) in the preparation example 9 was obtained at 52 to 60 C at 200 iimHg for 20 minutes with elimination distilled from 60 g of a 67% aqueous methanol solution. The material contained 60 after distillation % By weight formaldehyde, 3% by weight methanol and 37% by weight water.

100 g of the material was mixed with 1 mol of phenol at 50 ° C. to obtain a transparent solution (material).

Production example 14

200 g of liquid material, which had been obtained in Preparation Example were at 86 to 103 ⁰ C at atmospheric pressure for 50 minutes for elimination of 24.8 g of a 68% aqueous solution of methanol distilled. After the distillation, the material contained 65% by weight of formaldehyde, 2% by weight of methanol and 33% by weight of water. 100 g of the obtained material was mixed with 1 mole of phenol to obtain a transparent solution.

Production example 15

1.2 kg / h of methanol and 1.156 m ³ / h of air (air / methanol ratio

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(l / g) = 0.963) and the reaction was carried out at 560 ° C in the presence of a circular copper mesh catalyst (Diameter of copper wire: 0.2 mm; diameter of mesh: 0.83 mm) to obtain a gas.

The resulting gas was absorbed in water to obtain a liquid material containing 50% by weight of formaldehyde, 20% by weight of water and 30% by weight of methanol.

100 g of the resulting solution were at 103 C at atmospheric pressure distilled for 15 minutes with elimination of 27 g of a 56% aqueous methanol solution. After distillation, the material contained 68.5% by weight of formaldehyde, 11% by weight of methanol and 20.5% by weight of water.

100 g of the solution (material) obtained was mixed with 1 mol of m-cresol to obtain a liquid material mixed.

example 1

In a reaction vessel equipped with a stirrer, reflux condenser and a thermometer, 47 became 4 parts by weight of a phenol-formaldehyde material (Formaldehyde / phenol = 2 (in the molar ratio); water / phenol = 3.13 (in the molar ratio)) and 26 parts by weight Phenol introduced to adjust the formaldehyde / phenol molar ratio to 1.78. Calcium hydroxide (catalyst) was added to the pH value of the

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Adjust the reaction system to 8.5. The reaction was carried out at 100 ° C for 5 < Resole resin carried out.

was at 100 ° C for 50 minutes to obtain a

The obtained resin was diluted with water and poured into a

2 linter paper with a weight of 100 g / m impregnated.

10 sheets of the impregnated paper (prepregs) were stacked and stored at 150 ° C under a pressure of

ο 100 kg / cm pressed to obtain a laminate.

The obtained laminate was excellent in boiling water resistance and nearly showed no weight gain.

Example 2

The procedure of Example 1 was repeated in the same way, except that barium hydroxide was used in place of calcium hydroxide.

The laminate obtained was excellent in boiling water resistance and showed none Change in weight.

Example 3

252 parts by weight of the m-cresol-formaldehyde material obtained in Preparation Example 12 and 108 parts by weight

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m-cresol were introduced into the same reaction vessel, used in Example 1 to adjust the formaldehyde / m-cresol molar ratio to 2.0. Sodium hydroxide was added to the vessel as a catalyst to adjust the pH of the reaction system to 9.0.

The reaction was carried out at 100 ° C. for 60 minutes with maintenance of a resol. Using the obtained resole, a laminate was made in the same manner as produced in Example 1. The laminate had excellent resistance to boiling water, with it showed almost no change in weight.

Comparative example 1

188 parts by weight of phenol and 289 parts by weight of 37% formalin were in the same reaction vessel which was used in Example 1, while setting a formaldehyde / phenol molar ratio to 1.78, It was calcium hydroxide to adjust the pH added to 8.5.

The reaction was carried out at 100 ° C. for 120 minutes. The reaction mixture was then stirred at 600 mmHg for 60 minutes to eliminate 130 parts by weight of a dehydrated waste water solution to obtain dehydrated of a resin.

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Using the resin, a laminate was produced in the same manner as in Example 1.

Comparative example 2

94 parts by weight of phenol and 66.8 parts by weight of 80% paraformaldehyde were placed in the same reaction vessel which was used in Example 1 to adjust the formaldehyde / phenol molar ratio to 1.78. To this end, barium hydroxide was added to adjust the pH of the reaction system to 8.5.

The reaction was initiated at 100 C, but after Gelation occurred for 10 minutes due to rapid heat generation.

Comparative example 3

216 g m-cresol and 324 g 37% formaldehyde (formalin) (Formaldehyde / m-cresol = 2 (in the molar ratio), water / Formaldehyde = 0.6 (in weight ratio)) were in the same reaction vessel that was used in Example 1 den was, setting the formaldehyde / m-cresol molar ratio of 2.0 entered. Sodium hydroxide was then added to adjust the pH of the reaction system to 9.0.

The reaction was carried out at 100 ° C. for 120 minutes.

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The reaction mixture was then heated to 520 mmHg during
60 minutes with elimination of 150 parts by weight
a dehydrated waste liquid to obtain
dehydrated of a resin.

Using the obtained resin, a laminate was produced in the same manner as in Example 1. The ones in the Results obtained in Examples 1 to 3 and Comparative Examples 1 to 3 are in the table below summarized.

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Tabel

Example Example Comparison Comparison Comparison game 1 game 2 game 3 example 1 example 2 example 3

Conversion of
Phenol or m-cresol (mol%) 80.3 81.2 79.3 78.5-80.4

Conversion of

Formaldehyde (mol.%) 80.0 82.2 80.6 70.6 78.0 co * 1
Miscibility 190 220 10 41 0 Viscosity (cps)
(at 30 ° C) 150 120 140 120 280 σ σο properties
of the laminate

Resistance to boiling
Water (h) * ² >18>18> 18 '5 - 9

Change in size * ³ (%)

Longitudi- i ^ »

nal direction 0.13 0.20 0.18 0.62 - 0.68 ^ _n

Continuation of the table

Horizontal direction

0.35

0.41

0.33

0.88

0.96

Notes: * 1

CD OO O

O CD OO

«3 * 4

Amount of water (ml) at the time when water is added to 100 parts by weight of the resin and turbidity occurs (at 30 ° C)

Time (h) until swelling, which is caused by immersing the laminate in boiling Water is effected.

According to JIS K-6903

Measurement due to occurrence of gelation in Comparative Example 2 not possible

Example 4

In the same reaction vessel that was used in Example 1 had been, 7 were 6.5 g of phenol and 13 2.1 g of a mixture of phenol, formaldehyde, and methanol Water (formaldehyde / phenol molar ratio = 1.8; methanol / phenol molar ratio = 0.12; water / phenol molar ratio = 19.6) is entered. Then 0.6 g (COOH) 2 was added and the mixture was heated to 98 ° C over Heated for about 40 minutes with stirring and then further stirred for 120 minutes at 98 ° C. Then the mixture was stirred the reaction mixture at 520 mmHg for 7 5 minutes with elimination of 52.2 g of a dehydrated Waste solution and yielding 153.5 g of a weak yellow resin dehydrated.

Conversion of formaldehyde (%) 99 Conversion of phenol (%) 90

Softening point of the obtained

Resin ( ⁰ C) 96.3

Comparative example 4

In the same reaction vessel that was used in Example 1, 106 g of phenol and 74.3 g of 37% formalin were added. Thereafter, 0.45 g of (COOH) _{2 was} added thereto and the reaction was carried out at 98 ° C. for 200 minutes.

7 Π 9 8 U 7/1 0 6 8

The reaction mixture was at 520 mrtiHg for 180 Minutes with elimination of 63 g of dehydrated Drainage solution and yielding 115g of resin dehydrated

Formaldehyde conversion (%) 98

Conversion phenol (%) 90

Softening point of the obtained

Resin ( ⁰ C) 98

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Claims (11)

PATENT CLAIMS 1. Process for the production of phenolic resins by reaction of one or more phenols with formaldehyde in the presence of an effective catalyst for the reaction, characterized in that one or more phenols and the formaldehyde from derived from a material that contains one or more phenols and no more than about 6 moles of formaldehyde per 1 mole of the one or more phenols as a starting material, the material being dissolved by dissolution from formaldehyde in one or more phenols. 2. The method according to claim 1, characterized in that an amount of about 0.5 up to about 5 moles of formaldehyde per 1 mole of one or more phenols are used. 3. The method according to claim 1, characterized in that an amount of 0.5 to 3 moles of formaldehyde are used per 1 mole of one or more phenols. 4. The method according to claim 1, characterized in that the material is not further contains more than about 7 moles of water per 1 mole of one or more phenols. 7 0980 7/1068 5. The method according to claim 4, characterized in that the amount of water 0.05 to 4 moles per 1 mole of the phenols. 6. The method according to claim 1, characterized in that the material is not further more than about 7 moles of water and no more than about 7 moles of methanol per 1 mole of one or more of the Contains phenols. 7. The method according to claim 6, characterized in that the amount of water 0.05 to 4 moles per 1 mole of the phenols and the amount of the methanol is 0.05 to 4 moles per 1 mole of the phenols. 8. The method according to claim 1, characterized in that the formaldehyde is oxidized by air is obtained from methanol. 9. Material that can be used as a raw material for the production of phenolic resins is marked by essentially one or more phenols and from about 0.5 to about 5 moles of formaldehyde per 1 mole of one or more phenols. 10. Material according to claim 9, characterized by essentially one or more phenols, from about 0.5 to about 5 moles of formaldehyde per 1 mole of one or more phenols and about 0.05 to about 4 moles of water per 1 mole of the phenols. 709807/1068 2835132 11. Material according to claim 9 or 10, characterized by essentially one or several phenols, about 0.5 to about 5 moles of formaldehyde per 1 mole of phenols, about 0.05 to about 4 moles Water per 1 mole of phenols and from about 0.05 to about 4 moles of methanol per 1 mole of the phenols. 709807/1068