DE1545053C3 - Process for the preparation of polyether-penenol association products - Google Patents

Description

where the ratio of non-cyclic ether groups to phenolic hydroxyl groups in the Final product is 0.02 to 240.

2. The method according to claim 1, characterized in that the association products are formed, by the resole or novolak resin in the presence of at least a portion of the polyether in produces situ, then neutralizes the condensation catalyst and unreacted reactants removed.

3. Use of the association products produced according to claims 1 and 2 for production thermoset resins in the usual manner in the presence of aldehydes and catalysts or phenols.

th, are generally thermoplastic materials; those that have a significant proportion of phenolic Components are included, although they can also be thermoplastic, but optionally also lighter and more thermosetting.

Thus, according to the invention, resin-like products with novel combinations of properties can be produced produce in a way that was previously not possible with polyether and phenolic materials.

The expression "association" means that there is no chemical reaction in the present case acts, but that between the polymeric ether and the novolak or resol hydrogen bonds, electrostatic bonds, effects of secondary valence forces, etc. occur. Probably explains that Phenomenon of hydrogen bonding is the best type of reaction in the process according to the invention. This Type of reaction between the phenolic component and the polymeric oxygen ether component in the association products produced according to the invention can be represented as follows:

35

The invention relates to a process for the preparation of polyether-phenol association products from a polymeric ether and a novolak resin or resol (phenolic component), which are especially as adhesives or for the production of films, protective coatings or moldings and for Extrusion are suitable.

The inventive method is characterized in that one

a) I to 99 percent by weight of a polymeric ether with a molecular weight of 18,000 to 10,000,000 containing at least 400 non-cyclic aliphatic ether oxygen atoms, wherein account for a molecular weight of 100 0.5 to 3.33 ether oxygen atoms, and

b) 99 to 1 percent by weight of a novolak resin or resole containing at least 0.5 phenolic groups per Molecular weight 100 contains, contacts or mixes, the ratio of non-cyclic Ether groups to phenolic hydroxyl groups in the end product is 0.02 to 240.

The association products prepared according to the invention can, depending on the choice of starting compounds sticky, thermoplastic masses to hard, tough, thermosetting or thermosetting masses represent. Those association products which contain a substantial proportion of the polyether component The above explanations of the reaction mechanism are purely theoretical and do not represent any Limitation of the invention.

The term "polymeric ether" or "polyether" used here refers to polymeric materials understood how they. are defined in the claim. They preferably contain an average of 0.5 to 2.85 non-cyclic aliphatic ether groups each with a molecular weight of 100. The expression »non-cyclic aliphatic ether "includes only those ether groups that are in straight or branched chains of the Polyether molecules occur. For example, B. Polyethylene oxide has a recurring unit -CH2CH2O- in the polymer chain; the oxygen atom in this recurring unit is therefore a "non-cyclic aliphatic ether" group. On the other hand will be Ether groups that form part of an organic ring, such as. B. the oxygen atom in tetrahydrofuran or the oxygen atoms in dioxane, not included in the above definition. It is pointed out that that these values can of course only be average values, since the respective starting products usually represent mixtures. In the absence of suitable molecular weight determinations, The polyethers also have a reduced viscosity above 0.3 and a maximum of 100 in the for the. respective Polyethers are labeled with the best available solvents. The molecular weight can by common methods, such as. B. by ultracentrifuge, light dissymmetry or osmotic pressure determined will. The reduced viscosity can be determined with an Ubbelohde, Ostwald or similar Viscometer at a temperature range between 20

3 4

and 30 ⁰ C using such a low selects on the basis of resin concentration in a solution that an approximately linear relationship between the reduced viscosity and polymer concentration, between an infinite dilution and the concentration at which the reduced viscosity is determined, is created. The reduced viscosity is defined as follows:

L1l

'(T ₀ ) (C)

T = flow time of a polymer solution with a low concentration through a standard Ubbelohde viscometer,

To = flow time of the solvent through the viscometer,

C = concentration of the solution.

The preferred ratio of polyether and novolak or resol is between 90 and 5 Parts by weight of polyether and 10 to 95 parts by weight of novolak or resol. The association of a bigger one A proportion of polyether with a smaller proportion of phenolic compound creates modified polyether resins with novel valuable properties. The association of a greater proportion of phenolic Combination with a smaller proportion of polyether creates modified phenolic resins with novel ones valuable properties. A wide variety of novolaks or resols can be used. the Phenolic resins can be converted into tough and flexible materials through association with the polyether will. The phenolic resins can be thermoset or optionally thermoset by the presence of the polyethers can also be left thermoplastic. The polyethers can be used as deformable Insoluble materials with high softening points for use as pressure sensitive adhesives soft or slowly dissolving complexes containing controlled amounts of materials, such as cresol and hexachlorophene, release, be produced.

The process by which the components are brought into contact to form the association products is generally determined by the amount and nature of the starting materials, in particular the phenolic component. The method according to the invention is an "association without condensation", where the desired product is obtained once the specified components are mixed. As well as the thoroughness of the mixer as well as the completeness of the removal of the (possibly present) Solvents promote maximum conversion and thus valuable changes in properties.

The inventive method is suitable for the production of slowly soluble complexes that have a enable controlled release of bacteriostatic, insecticidal, fungicidal and surface-active materials. The process can also be used in the preparation of insoluble complexes which are used as gelling agents, pressure sensitive adhesives, flexible materials, stretchable packaging films and shapes, Sizing and finishing agent for textiles and detoxifying agents for phenolic, in biological Organisms present poisons are suitable.

The polyether component used is selected

(a) the solubility in special solvents,

(b) the thermoplastic processing possibilities

5 ^th * ^e:

(c) its inherent flexibility and toughness and

(d) economic considerations.

The polyether should expediently have an average molecular weight above 100,000. the upper limits of molecular weight are determined by the melt viscosity range for thermoplastic processing or thickening (i.e. the increase in viscosity due to a given concentration of the polymer dissolved in a solvent) by the concentration is effected to produce the desired gel strength, necessary to handle the various Ratios of polyether and phenolic component is necessary. Polyethylene oxide is used for aqueous solvents are preferred.

The method according to the invention can be carried out by touching polymeric! Ether and resol or novolak respectively; z. B. by simply dissolving the materials either in a common solvent or in different solvents which, however, are miscible or emulsifiable with one another, or - if so - Both the polyether and the phenolic component are solids - by dispersing the finely divided materials in common nonsolvents or gelling agents. The polyether and the phenolic material can still be mixed as a hot melt if its properties so allow at elevated temperature, or they can be used together on conventional thermoplastic devices, such as B. calenders, extrusions or two-roll mills, mixed or kneaded. The Mixing polyether and phenolic compound in a solution is often due to the precipitation of the obtained association product as a solid, which is easy to remove in the usual way, characterized.

The properties of the association products differ considerably from the correspondingly added ones Properties of the polyether and the phenolic component. This can e.g. B. be determined when the the two components are present in such a weight ratio that approximately equimolar amounts of both Components are present, d. i.e. if the number of

The non-cyclic ether groups present in the polyether are approximately equal to the number in the phenol component phenolic hydroxyl groups present. The term "equimolar" refers to the equivalent weights. Hence the basic reference point is the gram molecular weight of the polyether, which is 1 mole of the ether group, and the gram molecular weight of the phenolic compound, which is 1 mole of phenolic Hydroxyl group supplies. Suitable association products can be made with as little as 2 mole percent or less polyether or made with as little as 0.4 mole percent or less of the phenolic component. From this it follows there is a ratio of acyclic ether group to phenolic hydroxyl group in the association products between 0.02 and 240 ether groups per phenolic hydroxyl group.

In a particular embodiment of the invention, the polyether and the phenolic compound in Solution held, both in the manufacturing

process as well as the product obtained. It was found that a pH above 8 to 10 the Precipitation of an association product prevented from the solution, especially in the presence of an aqueous one Medium. The invention now offers various options for keeping the components in solution, from which solutions and from these then valuable films, protective coatings and adhesive coatings are made can be. It was found that various agents (hereinafter referred to as "inhibitors" or "solubilizing agents" denotes the precipitation of an association product according to the following Can prevent executions. These inhibitors include water-soluble ketones, z. B. acetone, methyl ethyl ketone, acetonylacetone; Monoalkyl ethers of alkylene glycols, preferably the lower monoalkyl ethers of ethylene glycol and propylene glycol, e.g. B. the monomethyl ether of ethylene glycol, Monoethyl ether of ethylene glycol; Alkali metal bases, such as B. the hydroxides, e.g. B. sodium hydroxide, potassium hydroxide; Alkali metal salts weaker Acids, e.g. B. sodium bicarbonate, sodium acetate, potassium carbonate, etc .; Ammonia and water-soluble amino compounds z. B. ethanolamine, ethylenediamine, triethanolamine, pyridine, piperazine, piperidine, trimethylamine, Triethylamine, triisopropanolamine. Other inhibitors are e.g. B. dioxane, diacetone alcohol, ethyl alcohol, Dimethyl sulfoxide, acrylic acid, acetic acid, hydrazine, alcohols in general.

The amount of inhibitor or required to avoid precipitation of the association product Solubilizing agent depends on several considerations such as: B. the particular one used Novolak or resole including their molecular weight, the number of free phenolic hydroxyl groups in the same, the concentration of the phenolic compound, the particular polyether used including its molecular weight, the number the ether groups in this and its concentration, the particular inhibitor or solubilizing agent chosen Means, and other factors. Generally, a solubilizing amount becomes the above Connections used, d. H. at least such an amount of inhibitor or solubilizing agent that sufficient to avoid precipitation of the association product. According to the invention, routine Easily try the amount of inhibitor or required to avoid precipitation solubilizing agent can be found.

It has been found that the above water-soluble ketones and monoalkyl ethers of alkylene glycols in an amount of about one third, based on the total weight of the solution, must be used when using polyethers, e.g. B. polyethylene oxide with a reduced viscosity of about 1.0 or more (measured at a concentration of 0.2 g polymer in 100 ecm of water at 30 ⁰ C) a precipitation is to be prevented. As the number of ether groups in the polyether decreases, smaller amounts of the above-mentioned ketones or glycols are required.
With inhibitors or solubilizing agents, such as alkali metal hydroxides, alkali metal salts of weak acids, ammonia, water-soluble amino compounds, the amounts of inhibitor that can be used are in such a range that a pH value of the solution (including the polymeric components) above 8 to 10 is maintained . The pH can easily be determined in the usual way, especially in the presence of an aqueous medium. The association product is then precipitated by adjusting the pH of the solution to 7.7 or less, preferably to a range from 2.0 to 7.7. Inorganic acids such as. B. hydrochloric acid.

The association product was precipitated from solution by incorporation of one of the above water-soluble inorganic bases, alkali metal salts of weak acids or organic bases prevented, an evaporation of the solution to dryness, such as. B. by air drying or under reduced pressure, and then curing the residue obtained at elevated temperatures Association product.

Although the inhibited solutions of polyethers and phenolic compounds are most economical when water is part of the liquid carrier, inhibited solutions can be formed without water. Most of the inhibitors listed for water systems are also effective under anhydrous conditions. When acetonitrile is the liquid medium, _g acetone is a useful inhibitor; is Dimethylform- * amide the liquid medium, then z. B. acetonitrile suitable for inhibition.

Various methods can be used to incorporate or add the inhibitor to the system will. The inhibitor can e.g. B. either with the polyether component and / or the phenolic component mixed prior to the formation of separate solutions containing said polymeric components will. It can also be added to a solution containing the polyether component and / or a Phenolic component-containing solution can be added before mixing the two solutions. If necessary, the two solutions may be mixed in the absence of the inhibitor and, under certain circumstances obtained precipitate then by adding z. B.

a water-soluble ketone or monoalkyl ether of an alkylene glycol to form the system. In this case, it is preferred that the precipitate not be dried prior to the incorporation of the above inhibitor used for dissolution. _f

Basic inhibitors, e.g. As alkali metal hydroxides, alkali metal salts of weak acids A, ammonia and water-soluble amino compounds are particularly suitable agents, the pH of the system to adjust to the desired range. Therefore, if such basic inhibitors are used to maintain the pH of the solution above 8 to 10, the subsequent acidification of the solution to reduce the pH to 7.7 or less causes precipitation. A precipitated product can also be redissolved by adding the basic inhibitor in such an amount that the pH of the solution is brought into the correct range, ie above 8-10.

The inventive method can also be carried out so that the resole or novolak resin is produced in the presence of the Polether. In the beginning, only part of the polyether can be used used and the remainder (in portions) added during the reaction. In this embodiment it is necessary that the polyether is well mixed with the various reaction components, for which purpose optionally a solvent is used. The phenol-formaldehyde condensation takes place as follows

customary, the use of acidic catalysts being preferred. The condensation takes place in the usual way Way with stirring in a vessel with a steam condensation system. The one admitted at the beginning The amount of polyether is usually limited to avoid overloading the device. It can an additional mutual solvent can also be used. For such purposes the named inhibitors, such as. B. acetone, which is also a common solvent for the polyether and Phenolic components can be particularly suitable. One therefore usually proceeds in such a way that one z. B. phenol, Aldehyde, condensation catalyst and the polyether (possibly only part of the same) with sufficient Mixes solvent with stirring. The mixture is then until (partial) condensation Heated to reflux, e.g. B. between 1 and 8 hours. Then the catalyst is neutralized, the excess Driven off reactants and the reaction mixture cooled to room temperature.

The association product can be produced by several processes, some of which have already been mentioned. be won. If a precipitate forms when the solutions are mixed, this can be known as Way, e.g. B. by filtering or decanting can be obtained. If there is only an incomplete mix Precipitation of the added polyether and the phenolic compound can result in a further yield Product can be obtained by treating the solution with an acid. For this purpose, hydrochloric acid is great suitable, and the pH range is suitably between 2 and 7.7. Was the precipitation in illustrated manner, for. B. by a ketone or a monoalkyl ether of alkylene glycol, inhibited, so can the association product obtained by drying the solution in air or under reduced pressure will. Also acidification of water-soluble amines, ammonia, alkali metal bases or alkali metal salts Solutions inhibited by weak acids are used to precipitate the product.

It is usually convenient to dry the precipitated product. This is done by air drying or the curing methods described above. Satisfactory results will also be obtained with one Drying the product achieved under reduced pressure.

The polyethers that can be used as starting material can be expressed as non-cyclic aliphatic oxygen ether groups (for the sake of brevity hereinafter referred to as "ether atoms" or "ether groups") each with a molecular weight of 100. As indicated above, this includes only the ether atoms in the straight or branched chains of the polyether molecule; does not include the oxygen atoms forming part of an organic ring in the polyether molecule. The number of non-cyclic aliphatic ether groups contained in the polyether, each with a molecular weight of 100, is, as stated, in the range from 0.5 to 3.33, preferably 0.5 to 2.85, in particular 0.5 to 2.3. Ranges from 1.0 to 2.3, in particular 1.5 to 2.3, ether groups per molecular weight of 100 are particularly expedient. With regard to the above ranges, the lower limit of 0.5 includes compounds such as phosphoric acid diethylene glycol polyester (0.54) and some methyl celluloses. The upper limit is given by polyoxymethylene, the simplest polyether that can be used; the value of 2.85 is given by a 50:50 copolymer of oxymethylene, oxyethylene and polydioxolane. The value of 2.3 is limited by polyethylene oxide. In this case, polyethylene oxide is having a reduced viscosity of more 0.5 (concentration of 0.2 g as the polymer in 100 cc of acetonitrile at 3O ⁰ C) very preferred. These polyethylene oxides are hard, tough, horny, resinous materials. The polyether component contains at least an average of 400 ether groups, preferably at least an average of 450,

ίο in particular 600 ether groups. In a very preferred one Embodiment, the polyether component contains at least an average of 1000 ether groups, this minimum limit being about the value at which the polyethylene oxide is a resinous compound of the type described above.

Suitable polyethers are e.g. B. the polyalkylene oxides, produced by the polymerization of ethylene oxide, propylene oxide, or epoxybutane and mixtures thereof; the polyoxyalkylene glycols and ethers thereof, e.g. B. by reacting ethylene oxide or propylene oxide and mixtures thereof with small amounts of hydroxyl compounds such as aliphatic alcohols, glycols, phenols, glycerol or sorbitol can be produced. Also resinous homopolymers of 1,2-alkylene oxides and resinous copolymers of a mixture of 1,2-alkylene oxides (with reduced viscosities of at least about 0.5; _t determined on a solution of 0.2 g of polymer in 100 cc of solvent, for. B. acetonitrile, at 30 ° C) are very suitable. As 1,2-alkylene oxides come into question z. B. Ethylene oxide, propylene oxide, the epoxybutane, the epoxypentane, styrene oxide and chlorostyrene oxide. Also suitable are polyethers obtained by reacting ethylene oxide, propylene oxide and other olefinic oxides with synthetic and natural polymeric materials, such as. B. the novolaks, polyvinyl alcohol, polyamides, starches, cellulose, partially etherified cellulose, carboxymethyl cellulose, partially etherified starch, carboxymethyl starch, polycarboxylic acids (monomers and polymers), polysulfonamides and polycarbamides, as well as polyethers made by reacting ethylene oxide and propylene oxide with the glucosides and sugars, e.g. B. methyl glucoside, sucrose or glucose were obtained.

Also suitable are polyethylene glycol and polypropylene glycol and ethylene oxide-propylene oxide mixed polymer glycols, those with a diisocyanate or a diepoxide, e.g. B. the diglycidyl diet of a bisphenol, were implemented to produce longer chain polyether components. The end groups of the Polyalkylene polyols and the higher molecular weight resinous homopolymers and copolymers and other polyethers are not critical to the invention; these can be carboxylic acid ester groups, ester groups inorganic acids, amides, amines and ether, halogen, acetal, hemiacetal, aldehyde or Be carboxyl groups. Hydrocarbon end groups of fatty acids can e.g. B. by ester, amide and Ether groups be bound. These same organically functional groups can also be called occasional or recurring substituents are present as side chains or in the main chain of the polyether occur as long as they do not lower the concentration of the ether groups too much.

In the following formulas I to VII some subgroups of polyethers (or their typical Structural units or groups) indicated which are suitable as starting materials according to the invention.

609 520/460

As indicated, the minimum molecular weight of the polyether component is 18,000. The following formulas do not, of course, include all useful subclasses of polyethers.

(D

in which A is an oxyalkylene radical, e.g. B. is an oxyethylene, oxypropylene, oxybutylene, oxytrimethylene, oxytetramethylene radical, etc., R is bonded to the oxygen atom of A and represents a hydrogen atom, a hydrocarbon radical, e.g. B. is an alkyl, alkenyl, cycloalkyl, aryl, alkaryl or aralkyl radical and R 'is bonded to a carbon atom of A and represents a hydrogen atom, halogen atom, e.g. B. chlorine, bromine, or a hydrocarbon radical, e.g. B. is an alkyl, alkenyl, cycloalkyl, aryl, alkaryl or aralkyl radical. Furthermore, R 'can stand for an alkoxy and aryloxy radical; and χ has a value such that the reduced viscosity of the polymer is at least 0.3.

R-fBt -EC3T-R '

(H)

OR

(HD

J
Y '

C (H) O-

(IV)

where B and C are different oxyalkylene radicals, such as. B. are an oxyethylene, oxybutylene, oxypropylene, oxypentylene or oxystyrene radical; R and R 'each represent a hydrogen atom, a hydrocarbon radical, e.g. B. an alkyl, cycloalkyl, alkenyl, aryl, aralkyl or alkaryl radical. Furthermore, R and R ', when bonded to the carbon atom of B or C, can represent a halogen atom, e.g. B. chlorine or bromine or an alkoxy or aryloxy radical; y and ζ are numbers with a minimum value of 1, and the sum of y and ζ is such that the reduced viscosity of the copolymer is at least 0.3.

CHOIR

where R each represents a hydrogen atom, an alkyl radical, e.g. B. a methyl, ethyl or propyl radical or one of the following groups:

(a) -fCH ₂ CH ₂ O), "Y

(b) - (CH ₂ CH ₂ CH ₂ O) ₁₁₁ Y

(c) - / - CH ₂ CHO \ Y

\ CH, J, "

in which Y stands for a hydrogen atom or a hydrocarbon radical, for example an alkyl or aryl radical and m is an integer which can vary in the groups represented by R; the polymer containing the above typical structural unit has a reduced viscosity of at least 0.3.

RO

40

45

CHOIR'

CH ₉ OR

where Y 'stands for a hydrogen atom or a carbon where R stands for a hydrogen atom and R and R' stands for a hydrogen radical, for example an alkyl or aryl radical, 50 each represents an alkyl group, e.g. B. a methyl, ethyl or and R can represent one of the following groups, e.g. B. Propyl group or one of the following groups:

(a) - (CH ₂ CH ₂ O) ₁₁₁ Y (b) - (CH ₂ CH ₂ CH ₂ O) ₁₁₁ Y (C) - / - CH ₂ CHO \ Y I CH ₃ J _n ,

55

60

in which Y represents a hydrogen atom or a hydrocarbon radical, e.g. B. an alkyl or aryl radical and m represents a different integer which can vary from one R to the other; the polymer containing the above typical structural unit has a reduced viscosity of at least 0.3.

(a) - (CH ₂ CH ₂ O) ₁₁₁ Y (b) - (CH ₂ CH ₂ CH ₂ O) ₁₁₁ Y (C) - / - CH ₂ CHO \ Y 1 CH ₃ ) _m

in which Y represents a hydrogen atom or a hydrocarbon radical, e.g. B. is an alkyl or aryl radical and m is an integer which can vary in the groups represented by R; The polymer with the above structural formula has a reduced viscosity of at least 0.3.

RO

CH ₁ OR

(VI)

CHOIR

where R each represents a hydrogen atom or an alkyl radical, e.g. B. a methyl, ethyl or propyl radical or one of the following groups:

(a)

- (CH ₂ CH ₂ O) ₁₁₁ Y

(b) -f CH ₂ CH ₂ CH ₂ O) ₁₁₁ Y

(c) -f CH ₂ CHO \ Y

I CH, ) _m

in which Y represents a hydrogen atom or a hydrocarbon radical, e.g. B. an alkyl or aryl radical, and m is an integer which can vary in the groups represented by R; the polymer represented by the above formula has a reduced viscosity of at least 0.3.

CH ₁ OR

- CH, CH0-

(VIl)

where for an alkyl radical, e.g. B. a methyl, ethyl or propyl radical or one of the following groups can stand:

(C)

- (CH ₂ CH ₂ O) ₁₁₁ Y
- (CH ₂ CH ₂ CH ₂ O) ₁₁₁ Y
-F CH, CH0 \ Y

CH ₃

where Y is a hydrogen atom or a hydrocarbon radical, e.g. B. an alkyl or aryl radical, and m is an integer which can vary in the groups represented by R; the polymer with the above formula has a reduced viscosity of at least 0.3.

Many of the polyethers described are known and readily available. The higher molecular weight polymers of ethylene oxide, propylene oxide, etc., copolymers of the same, and copolymers of ethylene oxide, Propylene oxide etc. with other lower olefin oxides e.g. B. the epoxybutanes, epoxypentanes and styrene oxide, can be produced by various processes.

Polyethylene oxide with a reduced viscosity of 1.0 or more, measured at 30 ° C and one Concentration of 0.2 g polymer in 100 ecm acetonitrile can be produced by many processes will; (The reduced viscosity, when measured in water, does not differ significantly from the viscosity measured in acetonitrile, in particular at a value of 1).

The production of polyethylene oxide is z. B. in Belgian patents 5 57 766, 5 57 833, 5 77 831 and U.S. Patents 29,71988 and 3,167,519 described. The manufacture of other suitable polyethers can be found in US Pat. 27 06 182 and 27 06 189 can be taken. Usable novolaks are e.g. B. in U.S. patents 26 10 955, 27 44 882 and 27 54 335. Their manufacture is well known, as is their manufacture of resoles. Only partially or fully cured resins can be used. According to the invention have association products made from polyethers with novolaks and resols a wide range of valuable properties. The particular combination of properties depends largely on the ratio of polyether to phenolic components and their special nature. With Polyethylene oxide and novolak or resole resin as components of the association product are the Properties of the final association product are determined by considering various factors.

Refractory or thermosetting association products can be made using a major proportion (e.g. 70 to 95 percent by weight) of the phenolic component and by having the mixture in the presence a basic catalyst is heated under pressure. The association products produced in this way have properties compared with conventional phenolic resins better mold release properties and wider applicability in molding. From it manufactured deformed articles have greater flexibility, toughness and impact resistance as well as a lighter color. Furthermore, all of the benefits obtainable with these new resins are derived from the resin created without the need for fillers or lubricants, as is the case with conventional phenolic resins Case is. The toughness and transparency of the association products increase as the the proportion of the phenolic component increases. An extraordinary advantage of the association products with high Phenol content (e.g. up to 80 percent by weight of the phenol component) is based on the fact that they are on the usual Devices are easy to extrude. The same association products can also be effective Resin-like plasticizers are used for common phenolic resins and are compatible in all proportions.

Thermoplastic and partially thermosetting association products can be produced by using a large proportion (z. B. 30 to 90 percent by weight) of the polyether component are produced. In comparison with common polyether resins, such as. B. polyethylene oxide, the association products are much less water sensitive and more stable. The thermoplasticity of the association products is also favored by the polyether and phenol components are combined under acidic conditions.

The new association products can be in attendance or made with the addition of substantial or even predominant amounts of materials which themselves do not form part of the association product, provided that these materials do not have an inhibiting effect on the manufacture of the product. Such inert additives are solvents for the respondents and the tools already described; Fillers, such as calcium carbonate, are neutral Clays, mica, soot and wood flour; Plasticizers for the reaction components or reaction products, such as water, high-boiling simple alcohols, diols and triols; and dyes, pigments, surfactants Agents, humectants, dispersants and matting agents.

The association products prepared according to the invention can also be used for the abovementioned purposes can still be used for the following purposes: flexographic printing plates, records, Gears, ball bearings, seals, washing machines, pipe plugs, sealing rings, washers, shoe soles, Skis, tobacco boxes, humidifiers, flower pots, all kinds of flows, centrifugal pumps, pipes, solid rocket propellants, Additives to polishes and waxes.

The association products obtained according to the invention can be used for the production of thermoset materials, the z. B. can also be used for the purposes indicated above, cured will. For this purpose, an aldehyde and / or an aldehyde are added to them in the usual way prior to curing Catalyst or another phenolic component added.

In this processing method, the polyether and the partially condensed phenolic resin mixed by being in a common solvent or dissolved in separate but miscible solvents or suspended in nonsolvents or by melting the materials together on a thermoplastic processing device or kneaded. Several of these mixing methods can also be used. At a preferred methods are the polyethers and the phenolic resin in a common solvent dissolved, evaporated to dryness and then thermoplastically kneaded or molded. The mix of Polyether and phenolic resin is used for final curing with an aldehyde and a catalyst or mixed with another phenol and optionally customary fillers or colorants.

If highly elastic to elastomeric preparations are to be produced, it is preferred that those for the further condensation necessary components already when mixing the polyether with the phenolic resin to add. It is often difficult to incorporate after mixing, as a very tough, rubber-like mass is obtained into which other materials are incorporated with difficulty be able. On the other hand, if resilient but less elastomeric products are to be made, which is usually the case takes place at lower concentrations of the polyether, so can the polyether and the phenolic resin mixed together, dried and ground to a fine powder into which the others then Components to be mixed in later.

The present invention is illustrated by the following examples in which the polyether and phenolic components and the methods of making the association products have been varied to illustrate different embodiments of the invention.
example 1

This example illustrates the formation of an association product from a resinous polyethylene oxide and a phenolic resin having a variety of methylol substituents.

9.1 g of a polyethylene oxide with a molecular weight of about 250,000 were dissolved in a mixture of 121 g of water and 100 g of acetone. 63 g of a water-dilutable phenolic resin with several methylol substituents were combined with a mixture of 50 g of distilled water and 100 g of acetone. The two solutions were mixed together without precipitation of the association product, after which films from the solution were poured onto glass slides and allowed to air-dry. The films were then cured at a temperature of 150 ^° C. for 25 minutes. The films exhibited good adhesion, no tarnishing, swelling, or loss of adhesion or weight after standing in water overnight.

In a further preparation, the same water-dilutable phenolic resin with several methylol substituents was made to a polyethylene oxide solution in water with a total solids content of 8% (in the absence of the acetone inhibitor) added to make solutions containing the ratios of polyether to Phenol derivative between 90:10 and 10:90. In the absence of acetone, precipitation of the association product was evident in all of them ratios tested, but most noticeably at or near equimolar ratios.

Example 2

This example illustrates the preparation of association products from a resinous polyethylene oxide and uncured novolak resins with different average numbers of phenolic groups per molecule.

The resinous polyethylene oxide used had been prepared by bulk polymerization of ethylene oxide with Strontiummethylat as a catalyst at 120 ° C (reduced viscosity = 9.25 at a concen- tration _f of 0.2 g in 100 cc of acetonitrile). It became a %. Aqueous polymer solution (6.0% total solids) prepared, mixed with acetone and various novolak resins and the mixtures then ground on a system of cylinder rollers overnight in order to dissolve the remaining solid materials. The mixtures were then cast as films onto glass plates and cured for 1 hour at 15O ⁰ C. The mixture made with equal parts of polyethylene oxide and a phenol-formaldehyde resin having an average of 2 to 3 phenolic groups per molecule (novolak resin A) provided a film with excellent adhesion, flexibility, clarity and gloss. The material was very soft and rubbery and looked like a good, quick-setting adhesive. A second film made from a mixture of equal parts by weight of the same resinous polyethylene oxide and a phenol-formaldehyde novolak with an average of 5 to 6 phenol groups per molecule (novolak resin K) had the good adhesion, flexibility, clarity and gloss as the first film, but was very rubbery, sticky and much less viscous than the first film. Both films redissolved after stirring for 3 hours in water at room temperature.

The novolak resin A used above was prepared from a reaction mixture of 100 parts of phenol, 12 parts of an aqueous 35 to 40% formaldehyde solution and 0.1 part of lead acetate, which was ^{heated to 100 °} C. for 2 hours and then, after partial dehydration distillation, for 1 hour heated to 150 to 158 ° C. The novolak resin K was prepared from a reaction mixture of 100 parts of phenol, 72 parts of an aqueous 35 to 40% formaldehyde solution and 0.56 parts of oxalic acid, which was heated for 3 '/ 2 hours at 90 to 120 ⁰ C.

Example 3

This example illustrates the preparation of polyether-phenol association products from a resinous polyethylene oxide and a phenolic resole resin.

A resinous polyethylene oxide was prepared as a solution in trichlorethylene (5% total solids). to 200 g of this solution were 10 g of phenol-formaldehyde resin (Resole resin R), made with hexamethylenetetramine had been catalyzed, added. The resol material was obtained as a solution in 90 g of ethylene glycol monoethyl ether admitted.

After mixing for 6 hours on cylinder rollers, a light yellow, clear, gel-free solution was obtained. on Glass plates were cast a film (1 mm wet thickness) which was soft and air-dried after 5 days was slightly sticky. Curing for 30 minutes at 150 ° C converted the film to pliable, clear, not sticky, shiny, adhesive coating material around. In contrast, a similarly delivered but only a hard, very brittle coating produced using the resol resin, after it was hardened on the glass plate.

It was the solubility of the two films prepared above in a mixture of 31 parts of ethylene glycol monoethyl ether and 69 parts of trichlorethylene found by adding 0.5 g of the film to 102 g of solvent mixture Mixed for 24 hours at room temperature. It was found that the polyether modified An insolubility of 88.4% compared to 64.5% of the film in this solvent mixture Resolfilmes owned.

The resole resin R used in this example was prepared from a reaction mixture of 100 parts of phenol, 90 parts of an aqueous 35 to 40% formaldehyde solution and 5.63 parts of hexamethylenetetramine, which was ^{heated to 80 °} C. for 35 to 40 minutes.

The polyethylene oxide used in this example was produced by the decomposition of a higher molecular weight Resin produced by suspension polymerization in the presence of a calcium amide catalyst had been made using chlorine. After the chlorine treatment, the polymer had a reduced viscosity of 5.6 at a concentration of 0.2 g in 100 ecm Acetonitrile.

Example 4.

Using the same procedure and the same polyethylene oxide as in Example 3, association products containing equal parts by weight of polyethylene oxide and a phenol-formaldehyde resin (novolak resin C) were cast as films on glass plates. After air drying for 5 days, the films were almost non-tacky, soft and slightly cloudy. ^{After they had been cured at 150 °} C. for 30 minutes, the films became clear, slightly amber, soft and slightly sticky. Both the phenolic resin films modified with polyether resins and the unmodified, hardened, brittle phenolic resin films dissolved completely in the mixture of ethylene glycol monoethyl ether and trichlorethylene. Similarly, an association product made from equal parts by weight of the polyethylene oxide and another phenol-formaldehyde resin (novolak resin D) produced a pressure-sensitive adhesive coating which was completely soluble in a solvent mixture of ethylene glycol monoethyl ether and trichlorethylene. A comparative coating of novolak resin D, prepared in the absence of the polyethylene oxide, provided a very brittle, hard, glossy, poorly adhering coating after curing and was also soluble in the solvent mixture.

The novolak resin C used in this example was prepared from a reaction mixture of 100 parts of natural phenol (90% phenol, 10% o-cresol), 67 parts of an aqueous, 35 to 40% strength formaldehyde solution and 1 part of phosphoric acid, which took 3 hours heated to 90 to 120 ⁰ C, then treated with a mixture of 1 part of sulfuric acid and 20 parts of blown soybean oil at room temperature and dehydrated in the presence of 3.2 parts of barium hydroxide by distillation. The novolak resin D was prepared from a reaction mixture of 100 parts of phenol, 65 parts of an aqueous 35 to 40% strength formaldehyde solution, 0.2 part of ferric chloride and 1.2 parts of water, which was heated to 100 ° C. for 4 hours.

Example 5

This example illustrates the effect of component ratios and curing conditions on the solubility and heat resistance of the polyether-phenolic resin association products.

Acetonitrile solutions of the polyethylene oxide used in Example 4 and a phenol-formaldehyde resin in acetonitrile (novolak resin E) were mixed together so that the ratio of polyethylene oxide to novolak resin was 4: 1, 1: 1 and 1: 4, respectively. The precipitates formed when the solutions were mixed were left to stand overnight together with the mother liquor, after which the mother liquor was decanted off and the solids were washed with acetonitrile. The solids were dried in aluminum foil pans at 50 ^° C. and 1 mm Hg pressure to a constant weight. The yields of precipitate from the individual mixtures are given in the second column of Table 2.

Mixtures similar to the above with dimethylformamide as the inhibitor component were used to avoid this a precipitation of the association product produced. The films cast from these solutions possessed good adhesion to glass, excellent flexibility, fairly good clarity, good strength and a dry smooth surface.

Other association products were made from the same polyethylene oxide and novolak resin as above, using these components as dry materials - in some cases with the addition of dry hexamethylenetetramine; . cf. Table 1 - mixed and then deformed ² pressure and a temperature of 19O ⁰ C for 5 to 10 minutes to form sheets of 13.8 cm diameter in a press of 350 kg / cm. Portions of these plates were extracted with water at room temperature for 24 hours and the percentage of moisture uptake and insolubility determined.

609 520/460

Additional parts of these plates were prepared for 15 minutes, 4 from a reaction mixture of 100 parts

Hours and 20 hours ^{heated to 300 0} C and the percentage of weight loss determined. These data are given in Table 1.

The Novolak Resin E described above was

Table 1

Phenol, 68.25 parts of an aqueous 35 to 40% strength formaldehyde solution, 1.25 parts of oxalic acid and 0.7 Share water that had been heated to 100 ° C for 6 hours.

ratio of
Polyethylene oxide
to phenol. Novolak

% Yield
Precipitation,
based on the
total solids present

Properties of the hardened association products

% Water-% insoluble- weight loss after heating to 300 ^° C

absorption in water 15 minutes 4 hours 20 hours

1: 4
1: 1 «)

3:72)
0:13)
0: 1

17.3
71.5

41.5

454
549

47.9
48.4
1.01
1.01
1.00
1.00

99.4
98.9

99.6
99.7
100.0
100.0
100.0
100.0

98
9.7

3.5

14.2
8.2

20.3
17.7

16.7
17.1

24.6
23.1

17.1
17.9

= 6.5 percent by weight of hexamethylenetetramine, based on the total weight of the preparation, added. = 8.9 percent by weight of hexamethylenetetramine, based on the total weight of the preparation, was added. = 12.3 percent by weight of hexamethylenetetramine, based on the total weight of the preparation, added.

Example 6

This example illustrates the preparation of a polyether-phenolic resin association product from polydioxolane and a novolak resin.

Polydioxolane, produced by the bulk polymerization of dioxolane (ethylene glycol formal) at room temperature and a duration of 234 hours using boron trifluoride as the catalyst a melting point between 55 and 60 ° C and a reduced viscosity of 0.14 at one concentration 0.2 g in 100 ecm of water at 30 ° C. was dissolved in acetonitrile to form a 16.7% solution. Also an im phenol-formaldehyde novolak resin used in the previous example was also dissolved to a solution in acetonitrile (16.7% total solids). It made up a slight precipitate occurs when mixing equal parts by weight of the two solutions, which however redissolved when the mixture was agitated on cylinder rollers for 18 hours. From the resin solution A film was cast on a glass plate, air dried for 16 hours and then cured at 150 ° C for 30 minutes. The resulting clear amber film had good glass adhesion and tackiness pressure sensitive adhesive. If the film was extracted with acetonitrile for 24 hours at room temperature, so 53.4% was insoluble and the insoluble part absorbed 14.2% solvent.

35

40

45

Example 7

This example illustrates that the unsatisfactory results of the comparative experiments below the same conditions cannot be achieved when making a polyether-phenolic resin association product one of the polyether compounds preferred according to the invention is used.

According to Experiment C, 47 g of phenol, 34 g of 37% strength aqueous formaldehyde and 2.9 ecm of 1.0 N sulfuric acid were mixed and refluxed for 87 minutes. 6 g of hexamethylenetetramine and 60 g of resinous polyethylene oxide (molecular weight about 250,000) and 200 g of acetone were added to the mixture and mixed well in a mixer. The material was dried in a vacuum oven and, by molding for 20 minutes at 150 ° C. and a pressure of 70 kg / cm ^2, a sheet was produced which was clear, pliable, non-sticky and very stretchable. According to the water extraction test, the deformed plate contained 73.8% insoluble material with a moisture absorption of 50.9%. Tensile strength data obtained on a conventional testing machine are given below.

speed Tear resistance when breaking strain when breaking stiffness the stretch at the at the Stretch limit (kg / cm *) Stretch limit (%) (cm / min) (kg / cm *). 72.8 (° / o) 171 (kg / cm?) 0.5 53.1 84.4 168 214 367.9 5 84.4 103.8 214 290 12.5 103.8 103.5 290 200 25th 103.5 115.5 200 233 50 115.5 110.8 233 164 125 110.8 164

Example 8

Example 11

This example illustrates the preparation of a flexible polyether-phenolic resin association product ^; tes made from brittle polyether and phenolic resin components.

70 parts Polystyroloxyd (0.8 noncyclic oxygen ether groups per a molecular weight of 100; manufactured by bulk polymerization of styrene oxide at 9O ⁰ C and a duration of 2 hours) was mixed with 30 parts of novolac resin E (described in Example 5) in a Combined methyl ethyl ketone solution. The homogeneous solution was allowed to evaporate and a soft, putty-like product was obtained. This material was pressed for 10 minutes at a temperature of 13O ⁰ C under slight pressure between stainless steel plates. A practically homogeneous film was obtained which was stretchable and flexible and did not adhere to the steel plates.

Example 9

According to Example 10, 47 g of phenol, 34 g of 37% strength aqueous formaldehyde and 2.88 ecm of 1.0 N sulfuric acid were mixed and refluxed for IV2 hours. The reaction mixture was neutralized with lime water and 60 g of polyethylene oxide (molecular weight about 250,000) were added. The material was transferred to a conventional mixer and mixed for 2 hours with the occasional addition of acetone for ease of use. After drying the mixture in a vacuum oven, a sticky, rubber-like residue was obtained, which was ^{shaped for 20 minutes at 150 ° C. and 70 kg / cm 2} to give a plate which was rubber-like, sticky and very flexible. According to the water extraction test, the material had an insolubility of 85.1% and a moisture absorption of 117.8%.

Example 10

40

There were mixed 94 g of phenol, 67 g of 40% aqueous formaldehyde and 5.8 cc of 1.0 N sulfuric acid and heated for 1 hour at 97 ⁰ C to reflux. The mixture was partially freed from volatile components, then ^{cooled to 27 °} C. and mixed with 50 g of acetone to reduce the viscosity. 121 g of polypropylene oxide-ethylene oxide (prepared by polymerizing 75 parts of ethylene oxide and 25 parts of propylene oxide in the presence of an alkaline catalyst until the liquid product had a viscosity of about 21,000 cP at 38 ° C.) and 100 g of acetone were added and stirred until completely dissolved; the solution was then mixed with 12 g of hexamethylenetetramine dissolved in a mixture of acetone and water. After drying the solution in a vacuum oven, an extremely viscous liquid residue was obtained. A sample of this material was placed in an aluminum pan and heated for 30 minutes at 100 ⁰ C and then 45 minutes at 150 ⁰ C for the purpose of pre-cure. This material was then molded between chrome plates for 15 minutes at 15O ⁰ C and a pressure of 14 to 21 kg / cm ^2; the resulting sheet was clear, pliable, tacky, and moderately stretchable. On an Instron tensile tester, the material had a tensile stiffness of 121 kg / cm ² . The tensile stiffness at a tensile speed of 0.5, 2.5 and 25 cm / min was 23.7, 31.5 and 42.4 kg / cm ^2, respectively.

This example illustrates the preparation of a polyether-phenolic resin association product from an Phenol compound and a polyether compound having a molecular weight in the lower limit of that for molecular weight suitable for purposes of the invention.

94 g of phenol, 67 g of 40% strength aqueous formaldehyde and 5.8 ecm of 1.0 N sulfuric acid were mixed and refluxed for 1 hour. The mixture was partially freed from volatile components and 50 g of acetone and a solution of 121 g of a polyether with a molecular weight of about 20,000 (produced by condensation of a polyethylene glycol with a molecular weight of 6,000 with the diglycidyl ether of bisphenol A; reduced viscosity 0.45 at a concentration of 0.2 g was added into 100 cc of water at 3O ⁰ C) in 150 g of water and 100 g of acetone. 12 g of hexamethylenetetramine dissolved in water were mixed with the material and the mixture was dried in a vacuum oven, whereupon a cream-colored, gummy residue was obtained, which at a temperature of 150 ^° C. and gradually increasing pressure up to 140 kg / cm ² ½ hour long has been deformed into a plate. The cured panel showed signs of incompatibility. The material was transparent, slightly (slightly) flexible and non-sticky, but strength and ductility were considerably lower than in association products made with higher molecular weight polyether components.

Examples 12 to 34

Each of the 55 preparations shown in Table 2 was prepared as follows: Powdered phenolic resin was weighed. The appropriate amount of powdered polyethylene oxide was added to enough water to form a gel (about 3 times its weight in water). It was used: In Examples 12-34 polyethylene oxide having a molecular weight range of 3000000-4000000 (reduced viscosity of 45 at a concentration of 0.2 g in 100 cc of water at 30 ⁰ C); in Examples 12A to 34A polyethylene oxide with a molecular weight range of 7,000,000 to 9,000,000 (reduced viscosity 70 at a concentration of 0.2 g in 100 ecm of water at 30 ° C); and in Examples 13B, 15B, 16B and 18B to 23B polyethylene oxide having a molecular weight range from 500,000 to 800,000 (reduced viscosity 3.9 g in 100 cc of water at 30 ⁰ C at a concentration of 0.2). The phenolic resin was kneaded in a grinding machine at 100 ⁰ C. The polyethylene oxide gel was added to the phenolic resin on the device with the intermittent addition of small amounts of water to maintain the material in a workable condition. Milling was continued until a homogeneous mixture was obtained.

Each of the preparations was compression-molded between steel plates, and the obtained plates had one high strength, good gloss and toughness. The products with up to 20% polyethylene oxide showed a relatively low water sensitivity. Those with a higher polyether content, i.e. H. above 20% could be deformed just as well, but showed an increasingly stronger tendency to absorb water, when immersed in water for long periods of time

became. The deformed pieces of materials containing 20 or more parts of polyethylene oxide per 80 or less Parts containing phenolic resin were pliable at room temperature. Materials with less than 20% Polyethylene oxide was inflexible at room temperature, and inflexibility and hardness increased with it increasing the phenolic resin content. Ratios of polyethylene oxide to phenolic Resin up to 40:60 provided clear fittings with excellent shine.

Unlike most thermoplastics and unfilled phenolic resins can the polyethylene oxide-phenol association products prepared according to the invention on conventional compression molding devices such as those normally used for molding commercially available filled phenolic Molded preparations are used to be deformed.

Table 2

Examples of preparation (parts by weight)

No. Resole polyethylene resin

oxide F G

12, 12B 5 95 - 13, 13A, 13B 10 90 - 14, HA 15th 85 - 15, 15A, 15B 20th 80 - 16, 16A, 16B 30th 70 - 17, 17A 33-1 / 3 66-2 / 3 - 18, 18A, 18B 40 60 - 19, 19A, 19B 50 50 - 20, 20A, 20B 60 40 - 21, 21A, 21B 70 30th - 22, 22A, 22B 80 20th - 23, 23A, 23B 90 10 - 24, 24A 10 - 90 25, 25A 20th - 80 26, 26A 30th - 70 27, 27A 33-1 / 3 66-2 / 3 28, 28A 40 - 60 29, 29A 50 - 50 30, 3OA 60 - 40 31, 31A 70 - 30th 32, 32A 80 - 20th 33, 33A 90 - 10 34, 34A 50 (and 50 parts Resol resin H)

Resole Resin F was prepared as follows: A mixture of 100 parts phenol, 150 parts 37% Formalin and 3 parts of barium hydroxide was at a pressure of 350 mm Hg for 2 hours at 80 ° C Heated to reflux and neutralized with phosphoric acid. To the mixture was 5.5 parts of hexamethylenetetramine added and then at a pressure of 100 mm Hg to a mass temperature of 98 ° C dehydrated.

Resole resin G was prepared as follows: A mixture of 100 parts of cresol, 93 parts of 37% formalin and 4 parts of hexamethylenetetramine was ^{refluxed at a pressure of 200 mm Hg for 3} A hours at a temperature of 80 ° C. and then dehydrated at a pressure of 150 mm Hg to a mass temperature of 100 ° C.

Resole Resin H was prepared as follows: 100 parts phenol, 150 parts 37% formalin, and 0.75 parts Sodium hydroxide was at a pressure of 350 mm Hg for 2 hours at a temperature of 80 ° C heated to reflux, neutralized with phosphoric acid and at a pressure of 50 mm Hg on a Dehydrated mass temperature of 95 ° C.

Example 35

The following data show the increase in tensile strength of the association products of polyethylene oxide and phenolic resin with the increase in the polyethylene oxide content and the change in strength with the change in the kind of phenolic resin.

Deformed specimen

Impact strength (cm kg / cm ³ )

Product of Example 17
(1/3 polyethylene oxide to
2/3 resol resin F)
Product of Example 19
('/ 2 polyethylene oxide to
'^ Resole resin F)
Product of Example 27
(• / 3 polyethylene oxide to
^2/3 resol resin G)

157.6
396.8
272

With regard to resol resin F and resol resin G, see Examples 12 to 34.

Example 36

This example illustrates the preparation of a polyether-phenolic resin association product from

a polyether and a cresol-formaldehyde novolak resin, the novolak resin being prepared in situ. 54 g of m-cresol, 40 g of 37% aqueous formaldehyde, 3.5 ecm of 1.0 N sulfuric acid, 100 g of ethanol and 10 g of polyethylene oxide (molecular weight about 250,000) were mixed and heated to 87 ° C. for 1 hour 45 minutes . The mixture was partially freed from volatile components and a further 60 g of polyethylene oxide were added. The mixture was converted into a homogeneous rubber-like mass on a "Brabender" plastograph. After drying in a vacuum oven, a soft, rubbery, gray residue was recovered; 30 g of this material were molded for 30 minutes at 150 ° C. and 35 kg / cm ^{2 pressure.} The molded plate obtained was semi-transparent, bright yellow, soft, very flexible and could easily be creased. When the product was stretched by hand, it was found to have excellent recoverability.

Examples 37 to 41

These examples illustrate the preparation of association products from a high molecular weight Polyethylene oxide and a resole, the preparation of the resole being carried out in situ.

The proportions of phenol, formaldehyde and barium hydroxide condensation catalyst given in Table 3 were placed in a still and added to this mixture in small amounts Polyethylene oxide (molecular weight range 3,000,000 to 4,000,000; reduced viscosity 45 at a Concentration of 0.2 g in 100 ecm of water at 30 ° C) was added. During the addition of polymer small amounts of water added, as to maintain a uniform polymer dispersion was necessary.

The reaction mixtures were refluxed at 355 mm Hg pressure for 2½ hours at a temperature of 80 ° C. Then the obtained mixture was neutralized with phosphoric acid and 5.5 g Hexamethylenetetramine added. The pressure in the distillation system was reduced to 25 mm Hg and the mixture obtained is dehydrated at a kettle temperature of 80 ° C.

The olive-green, rubber-like mass obtained was transferred to a two-roll mill at 100 ° C, ground and processed into foils. During the rolling the material turned yellow and settled process gradually in the manner of a vinyl resin. The product made into films could be removed after removal Grind out of the device and cool slightly. If the products were compression deformed between steel plates, thus panels with high strength, good gloss and toughness were obtained.

Examples 42 and 43

These examples differ from Examples 37-41 in that a novolak resin is in situ will be produced.

As in the previous examples, the proportions of phenol, formaldehyde, oxalic acid condensation catalyst and polyethylene oxide polymer (molecular weight range 3,000,000 to 4,000,000; reduced viscosity of 45 at a concentration of 0.2 g in 100 ecm of water at 30 ⁰ C) mixed together, the mixture heated to reflux for 4 hours at atmospheric pressure and then dehydrated at a kettle temperature of 160 ° C. The mixture obtained was processed into foils on a roller mill and ground. While milling, 10 grams of hexamethylenetetramine was added and mixed thoroughly with the material. Deformed films with high strength, good gloss and toughness were produced.

Table 3

At- Initial reaction mixture in g

game phenol 37% aq. Kataly- Polyethylene-

No. CH2O sator oxide

37 100 150 3 ^a ) 10 38 100 150 3 ^a ) 15th 39 100 150 3 ") 20th 40 100 150 3 ^S ) 30th 41 100 150 3 ^a ) 50 42 100 69 0.55 b) 25th 43 100 69 0.55 b) 15th Λ = Ba (OH) 2 ■ 8 H2O. ti \ = Oxalic acid.

B) The mixtures given below were mixed by grinding, processed into films, granulated and mixed to form molding materials:

Product of example 12 85 - - Product of Example 13 - 85 - Resole resin F ¹ ) - - 85 Spruce wood flour 65 65 65 lime 7th 7th 7th Stearic acid 3 3 3

') Cf. the resol resin F. described in Examples 12 to 34.

A sample of each preparation was compression molded and tested for impact resistance; the results were as follows:

Usage examples

A) A mixture of 85 parts of the product of Example 15, 65 parts of spruce wood flour, 7 parts lime and 3 parts of stearic acid was ground and processed on a two-roll mill from 100 ⁰ C to form films. The sheet from the roller was air-cooled and granulated. A bottle stopper was made which was opaque and excellent in detail.

Deformed product

Izod impact strength cm kg / cm notch

A.
B.
C.

1.85
1.85
1.52

C) The product of Example 19 was extruded through an annular opening by using a Schnekkenpresse with a cylinder temperature of 100 ⁰ C and a die temperature of 130 ⁰ C. The extruded material was pliable and could be stretched by further cold stretching.

While common phenolic resin molding materials involve the incorporation of lubricants such as. B. stearic acid, require to avoid sticking in the mold, the inventively produced, Deformable resins do not contain lubricants and can be easily removed from the mold. All of the unfilled molding materials made of polyethylene oxide and described in Examples 12 to 34 Phenolic resins do not cause any problems of mold sticking at all.

D) The following table shows that deformed association products of polyethylene oxide and phenolic resin approximately equivalent tensile strengths such as polyethylene and impact strengths to those of conventional phenolic molding materials are superior to own.

Table 4

Deformed preparation of Example 17

Polyethylene

Density; g / cm * 1.270

Impact resistance; 157.6
cmkg / cm ³

Tensile strenght; kg / cm ² 92

Strain; % 50

0.918 180

126 600

E) 50 parts of polyethylene oxide and 50 parts of Resole Resin F (see Examples 12 to 34) were by the process of Examples 14 to 36 are ground together. A commercial yellow turned on the grinder Pigment added until the desired shade of yellow was obtained. The material easily slipped into a pressure deform bright yellow bottle cap with excellent gloss.

609 520/460

A second preparation of 15 parts of polyethylene oxide and 85 parts was made by the same procedure Resole resin F produced and achieved equally good results.

F) The granular product of Example 38 was molded for 60 seconds at 140 kg / cm ² and 18O ⁰ C in a mold for a bottle screw cap. The fitting screwed out of the mold easily, was clear, yellow, inflexible, and tough, and the screw grooves and other details were excellent. The granular preparation of Example 19 was compression molded in the same closure mold. The molding was pliable, light brown, opaque, and excellent in detail. It did not become brittle even at temperatures as low as - 60 ° C.

G) A mixture of 50 parts of the product from Example 38 and 48.5 parts of spruce wood flour was obtained and 1.5 parts of calcium stearate, milled, processed into films on a device, granulated and shaped into a bottle closure as in the above examples. The buckles were deformed opaque and excellent in details.

Comparative experiments

A) This experiment illustrates the unsatisfactory results when an association product is obtained from a Phenolic compound and a low molecular weight polyether compound is produced.

20 g of polyethylene glycol (molecular weight about 6000) were mixed with 20 g of phenol-formaldehyde novolak resin (Novolak resin E from Example 7) mixed and the mixture melted and with the addition of 2 g Hexamethylenetetramine stirred. After about 5 minutes more stirring, the solution began to solidify, which was evident from an increase in viscosity. Then the mixture was on an aluminum foil poured and heated for further heat curing. The orange-yellow film obtained was pliable and sticky but could not be quickly bent or stretched without breaking.

B) This experiment illustrates the unsatisfactory results when an association product of a Phenolic compound and a polyvinyl ether is produced.

47 g of phenol, 34 g of 37% strength aqueous formaldehyde and 2.9 ecm of 1.0 N sulfuric acid were mixed and refluxed for 1 hour. After removal of the volatiles (25 minutes under vacuum), 6 g of hexamethylenetetramine was added to the cooled mixture. The mixture was placed in an apparatus having blade mill and 214 g of a Polyvinyläthylätherlösung in heptane (28% total solids; reduced viscosity of 3.6 at a concentration of 0.1 g per 100 cc of benzene at 2O ⁰ C) mixed. After mixing was complete, the material was dried in a vacuum oven. The resin product obtained was tough, elastic and exhibited good adhesion to the tray in which it was located. A 19 cm plate was produced from a sample of this material using 70 kg / cm ² pressure and 150 ^° C. by deforming it for 20 minutes, which was pale yellow, opaque, pliable and somewhat stretchable

ίο was. The product was found to be a partially incompatible mixture was. When part of the plate was extracted with heptane, it disintegrated Completely. Another part of the plate was placed on a conventional device for measuring tensile strength tested its physical properties and obtained the following results:

speed tensile strenght the elongation (cm / min) (kg / cm ² ) 0.5 2.16 5 3.65 12.5 4.43 25th 5.22 50 5.79 125 6.91

C) This experiment illustrates the unsatisfactory results when using a polyether-phenol association product is made from a phenolic resin and a carboxymethyl cellulose.

46 g of phenol, 34 g of 37% strength aqueous formaldehyde and 2.9 ecm of 1.0 N sulfuric acid were mixed and heated to reflux for 2 hours. The mixture was left under vacuum for 75 minutes Freed volatile materials and then 60 g of carboxymethyl cellulose, 150 g of acetone and 6 g of hexamethylenetetramine admitted. The mixture was stirred for 40 minutes but remained heterogeneous. After drying After mixing in a vacuum oven, it was found that the resulting dried material was a hard, contained brownish, horny material and a brittle, easily crumbly material. These two types of Material was roughly separated and plates were deformed from each part. The intolerance in both Platten was quite evident; they were very weak and easy to crumble.

The carboxymethylcellulose used in this experiment had a viscosity of 25 to 50 cP for a 2 ° / o concentration in water at 25 ⁰ C. The polymer contained an average of 0.7 carboxymethyl groups per glucose unit or 0.35 ether groups per a molecular weight of 100 .

Claims (1)

Patent claims: 1. Process for the production of polyether-phenol association products, characterized in that one a) 1 to 99 percent by weight of a polymeric ether with a molecular weight of 18,000 up to 10,000,000, which contains at least 400 non-cyclic aliphatic ether oxygen atoms, where there are 0.5 to 3.33 ether oxygen atoms for a molecular weight of 100, and b) 99 to 1 weight percent of a novolak resin or resole containing at least 0.5 phenolic groups contains, brings into contact or mixes per molecular weight 100,