DE818696C - Process for the production of resinous polyesters - Google Patents

Description

Process for making resinous polyesters The invention refers to a method of making new artificial resinous ones Products that have a particularly favorable combination of physical and chemical Have properties. The new artificial ones made according to the invention Resin-like substances are polycondensation products, which have their chemical character of linear aromatic polyphosphates in which the phosphorus atoms in the long chain and attached to two chain-forming aromatic hydroxyl groups and sit on a branched aromatic hydroxyl group.

These new substances are insoluble in water, alcohol, ether and paraffin, but soluble in chloroform, dioxane and mixtures of benzene and alcohol in certain proportions and in various other mixtures of organic liquids which individually do not have any dissolving properties on these substances. They can also be dissolved in relatively small parts of benzene and toluene oil to give concentrated solutions. The solutions of these resins are clear, translucent, viscous liquids. The new resinous products are soft and melt when heated high enough. They do not have any properties that harden through heat, but they can be made infusible by appropriate chemical modification. When volatile solvents are used, the resins can be used by spraying, painting or dipping as a covering material for metals, glass, wood, rubber and many other materials, and the covering layers so produced have a high gloss and good flexibility and, if they are for If the covering is used for metal surfaces, protect them against corrosion. These resins have extremely good clarity, Min high refractive power; they are mostly faintly colored or colorless and are extremely resistant to the action of water and acids. They have low flammability and can be heated to about 3w ° without decomposition occurs. Certain resins of this type are also non-flammable if they are decomposed by heating in the flame. At room temperature the resins have different strengths, depending on the substances have been used for their preparation position ".

The new resinous substances can also be used as cements for adhesive purposes. Thus they can be used as clear: colorless adhesives for glass, especially bearing in mind that certain selected resins have the same refractive index as glass. They can also be used to join metals, rubber, wood and other fabrics. These resins are excellent binders for insoluble fillers, pigments, and the like. By incorporating these materials into the synthetic resinous materials prepared according to the invention at room temperature above the softening point, thermoplastics of high toughness and good mechanical properties are obtained for the production of gramophone records and similar objects, because they can be shaped with extremely sharp contours.

These resins are compatible with many other organic film-forming substances. For example, they are industrial in all proportions. produced nitrocellulose and in certain proportions also with ethylcellulose, polyvinylchloride and various other polymers. If necessary, plasticizers for these film-forming substances can be kept in solution along with the new artificial resinous substances. Coverings made using these new synthetic resinous substances together with nitrocellulose are less "easily flammable" than those made from nixrocegu cheese alone, in other words these new, synthetic resinous substances have an inflammation-retarding effect on the nitrocellulose . .

According to the: invention; production takes place. of the new artificial resinous substances by condensation of aryloxypbosphoryl dichlorides with aromatic dioxyne bonds, the two hydroxyl groups of which are bonded to the nucleus and are located on non-adjacent goble atoms .

# Preferably. find 'the aryloxyphosphoryl dichloride and the axoomatic dioxy compounds in equimolecular amount application.

This condensation is expediently carried out by heating, rather mixing the 'mentioned compounds until' the required resinous properties in the reaction mixture. have developed. The condensation is expedient several hours of heating carried out at temperatures that increase to the extent that how the condensation progresses, from 100 to 180 degrees at the beginning of the condensation and from 190 to 24o ° at the end. It is advisable to stir the reaction mixture slightly, especially when their viscosity begins to increase. It goes without saying that the entry of moisture is prevented during the reaction. Appropriate the condensation is carried out in a neutral atmosphere, for example under nitrogen or carbon dioxide. The condensation also takes place expediently at normal printing, however, it is advantageous to print one after the condensation has ended Apply negative pressure to remove traces of hydrogen chloride from the viscous product remove. In certain cases it is useful when the formation of hydrogen chloride supporting catalysts such as metallic tin, calcium chloride, boron trifluoride and zinc or aluminum chloride, the latter two in only very small quantities, are present to help carry out the condensation.

The condensation mentioned can take place in that aryloxyphosphoryl dichloride is treated with aromatic dioxy compounds in a common solvent, this solvent also containing a substance that absorbs hydrogen chloride.

Examples of common solvents are: ether, benzene, Chloroform. The substance that absorbs hydrogen chloride can, for example, be a binary one Be amine, e.g. B. pyridine.

The novel resinous materials made according to the invention can be cleaned if desired. For example, they can be dissolved in benzene and precipitated in these solutions by adding ether. The resulting precipitate, which accumulates in the form of a thick ethereal liquid, can be washed further with ether and then dried under normal or reduced pressure. If it is desired to further reduce the acid number of these resins, this can be done by treating the solutions of the resins in an organic solvent with anhydrous sodium carbonate.

The new synthetic resins according to the invention have a structure which includes the following recurring group: In this formula, R 'denotes the aromatic radical present in the aryloxyphosphoryl dichloride. R "is the aromatic radical which is present in the aromatic dioxy compound mentioned.

The aromatic dioxy compounds mentioned, both of which are hydroxyl groups are on non-adjacent carbon atoms, one or more aromatic Have nuclei in their molecule. In the latter case, their hydroxyl groups expediently be present in two different cores, for example in the p or m-position to one another in a monocyclic dioxy compound or in the 2: 2'- or .4: 4'-position in the case of a diphenyl derivative. Dioxynaphthalene compounds can also be used Find application.

As aryloxyphosphoryl dichloride, for example, phenoxyphosphoryl dichloride, p-chlorophenoxyphosphoryl dichloride or o-chlorophenoxyphosphoryl dichloride application or any of the following new compounds: 2: 4-dichlorophenoxyphosphoryl dichloride, 2: 4: 6-trichlorophenoxyphosphoryl dichloride, 2: 4-dibromophenoxyphosphoryl dichloride, o-methylphenoxyphosphorylphosphoryl dichloride or 2-methyl-4: 6-dichlorophenoxyphosphoryl dichloride. However, mixtures of isomers or variously substituted aryloxyphosphoryl dichlorides can also be used be used. These compounds can be obtained by treating phenol, p-cresol, 2: 4-dichlorophenol, 2: 4: 6-trichlorophenol, 2: 4-dibromophenol, o-chlorophenol, o-cresol or 2-methyl-4: 6-dichlorophenol or mixtures of these substances in the case of increased Temperatures with more than one mole. Part of phosphorus oxychloride can be produced, if desired in the presence of a catalyst until the whole amount of aromatic present Dihy droxy connection is used up.

As the aromatic dioxy compounds, both of them are hydroxyl groups are on non-adjacent carbon atoms, for example, can be used be: hydroquinone or resorcinol or chlorinated hydroquinone or dioxynaphthalene or dioxydiphenyls, for example 2: 2'-dioxydiphenol, 4: .4-dioxydiphenyl or chlorinated dioxydiphenyl.

Some embodiments of the invention are given in the following examples. Example i A mixture of equimolecular amounts of phenoxyphosphoryl dichloride (boiling point 2440) and hydroquinone is heated on an oil bath with a glass vessel equipped with a slowly operating stirrer. A branch pipe is provided on this apparatus, one end of which leads to a liquid which absorbs hydrogen chloride. The contents of the boiler are protected against the ingress of moisture by using a calcium chloride tube. The evolution of hydrogen chloride starts when. the bath temperature is about 12o to 1300 , and condensation proceeds at this temperature for a few hours, the reaction mixture gradually turning into a clear liquid, the viscosity of which increases with the passage of time. The bath temperature is gradually increased to 205 to 2150 in order to maintain sufficient fluidity in the reaction mixture to allow the condensation to proceed. The heating is interrupted after a total heating time of 20 to 26 hours, after which the evolution of hydrogen chloride has practically ceased and after the viscosity of the reaction mixture no longer rises at 250.

The resulting raw resinous product is poured out of the vessel while it is still liquid and allowed to cool at room temperature. It is then in the form of a straw-colored transparent resin, which has good adhesion properties to glass and metals. The softening point is determined by the ball and ring method and determined to be 6o0. This fabric has remarkable cold flow properties. The acid number of the crude resin is 12 and it contains 0.1 percent by weight of unreacted hydroquinone and phenoxyphosphoryl dichloride. A sample of the crude resinous product is purified by dissolving it in benzene and the resulting solution is then extracted with ether. This removes practically all of the impurities that are initially still present, and the acid number is reduced. In addition, all of the benzene is removed. The extraction residue contains a sufficient amount of essential substance to hold back a swollen layer of liquid, which is clearly separated from the overlying layer of the used ether. This swollen residue, which is still liquid, is brought into solution in a benzene alcohol mixture, and a small excess of anhydrous sodium carbonate is added. This mixture is allowed to stand for about an hour. As a result of this treatment, after drying under reduced pressure, a resinous product with an acid number of 2 is formed. Before its treatment with sodium carbonate, the dry, cleaned resin has the following composition: carbon 57.8%, hydrogen 3.6%, phosphorus 12.2%. Calculated for the compound C6H50-P (= 0) -OC6H40- or C1QH904P the carbon content is 58.0 / 0, the hydrogen content 3.20 / 0 and the phosphorus content 12.50 / 0. Example 2 An equimolecular mixture of p-chlorophenoxyphosphoryl dichloride (boiling point 2650) and hydroquinone is heated under a nitrogen atmosphere in a kettle, similar to that described in Example i. The bath temperature at which condensation starts is, 13o to i40 °, and the heating is continued for 12 to 15 hours, wherein the temperature is increased to 205 to 2i5 °. After that, the condensation seems to be complete. The raw, transparent resin is almost colorless and forms a hard, shiny and very tough coating on metals. The softening point is 80 ° and its acid number is 14. If this substance is cleaned in the manner indicated in Example i and treated with anhydrous sodium carbonate, its acid number is o. If a piece of this resin is removed in an open flame, the substance does not burn further when it is removed from the flame. The plastic adheres well to metal and glass. Example 3 An equimolecular mixture of 2: 4-dichlorophenoxyphosphoryl dichloride (boiling point 138 ° at 1.6 mm) and hydroquinone is heated under a stream of nitrogen for 10 hours, the bath temperature from 130 to 135 ° at the start of condensation to 210 to 220 ° at the end of the condensation is increased. This condensation is carried out with the exclusion of moisture. The resulting raw, non-flammable resin has an acid number of 8 and a softening point of 10 °. This resin is somewhat harder than the resin obtained according to Example 2 and has better flame-extinguishing properties in mixtures with nitrocellulose. Otherwise, it is similar in its appearance and its properties to the resin prepared according to Example 2. EXAMPLE An equimolecular mixture of 2: 4: 6-trichlorophenoxyphosphoryl dichloride (melting point 68 to 70 °, boiling point 118 ° at 0.1 mm) and hydroquinone is heated with exclusion of moisture in the manner described in Example i, the bath temperature at the beginning of the Condensation is 160 ° and at the end of the same is increased to 195 to 200 °. The required reaction time is 10 hours. The raw resin is straw-colored and has a softening point of 115 °. It is non-flammable and, when mixed with nitrocellulose, has greater flame-suffocating properties than the resin produced according to Example 3. Example 5 An equimolecular mixture of phenoxyphosphoryl dichloride and 4: 4-dioxydiphenyl is processed in the usual way, a stream of nitrogen being passed over the stirred reaction mixture. The resin is brown in color and transparent in thin films. It results in hard and tough coatings that adhere excellently to metals and glass. These coverings have an extremely good resistance to dilute mineral acids. The softening point of these resins is 10 °.

Example 6 An equimolecular mixture of p-chlorophenoxyphosphoryl dichloride and 4: 4'-dioxydipheiiyl is processed in the manner described with the addition of boron trifluoride diacetate, based on the total weight of the reaction mixture, using a stream of nitrogen and with the exclusion of moisture. The condensation begins at a bath temperature of 180 °. However, in order to maintain the condensation, the presence of the boron trifluoride catalyst is required. The temperature at the end of the heating time of 12 hours is 200 °. The raw resinous product has a softening temperature of i25 ° and, to a large extent, has a deep wine-red color. Thin films of this material are clear and pink in color. They form hard and tough deposits on metallic surfaces. Example 7 O-cresoxyphosphoryl dichloride (boiling point 256 °) is processed in place of the phenoxyphosphoryl dichloride in the manner indicated in example i, nitrogen being passed over the reaction mixture. ] Otherwise, the implementation takes place in the same way as in Example i. The resulting almost colorless, translucent crude resin softens at 75 ° and has an acid number of i i. It is a little harder than the resin described in example i and does not flow in the cold. When a piece of this resin is heated in an open flame, it burns faintly with a glowing flame when it is withdrawn from the flame. Example 8 A mixture of o-chlorine, p-chlorine and 2: 4-dichlorophenoxyphosphoryl dicloride, which contain -5.8% hydrolyzable chlorine, is mixed with hydroquinone in such a ratio that for each molecule of a chlorinated phenoxyphosphoryl dichloride one molecule 1 -Lydroquinone is present, heated for 18 hours in a stream of nitrogen, the bath temperature being increased from 110 to 23o ° in the usual manner. The resulting resin softens at 100 °, and when it has been cleaned and treated with sodium carbonate in the trip described, it has an acid number of i. The appearance, the physical and the non-flammable properties are similar to the resin prepared according to I3example3. EXAMPLE 9 An equimolecular mixture of p-chlorophenoxyphosphoryl dichloride and resorcinol is heated for 20 hours in the manner indicated in Example 1, the temperature being increased from 165 to 195 °. The corresponding raw transparent resin is reddish-brown in color and has excellent adhesion to glass and metal. The softening point is 55 ° and the resin has an acid number of 28. It is somewhat harder than the resin produced according to Example i. Example 10 An equimolecular mixture of 2: 4-dibromophenoxypliosphoryl dichloride (boiling point 122 °) and hydroquinone is heated for 13 hours in a stream of nitrogen, the temperature being increased from 95 to 200 °. The resulting raw resin softens at 10 °, is pale straw-colored and has an acid number of 14. The hardness and adhesiveness of this resin is the same as that prepared according to Example 3, and it is similarly non-flammable. Example ii A mixture of 10,000 g of 2: 4-dichlorophenoxypliosplioryl dicloride and 3939 hydroquinone is heated on a metal bath in a glass vessel under a nitrogen atmosphere, the reaction vessel being provided with a stirrer. The bath temperature is held at 130 to 16o ° for 6 hours and then at 18o to 195 ° for 10 hours. After this time, the evolution of hydrogen chloride has practically ended. The reaction vessel is then connected to a vacuum pump and kept at a temperature of 170 ° to 180 ° for 1 hour under reduced pressure. The resulting resinous product is poured onto a cold aluminum plate and, after cooling, broken into pieces. The resin has good clarity, is pale straw-colored when it is in large quantities, but practically colorless in thin pieces. The acid number of this product is ii and the softening temperature is 104 °. After it has been dissolved in benzene and washed with ether, the acid number after drying is 8 and the softening temperature is 100 °.

The dry, purified resin has the following composition: carbon 45%, hydrogen 2.5%, phosphorus 9.2%, chlorine 22.6 0/0. The theoretical values for C12 C6 H3 O-P-O-O C0 H4 O or C12 H7 C1204 P are: carbon 45.4 0/0, Hydrogen 2.2%, phosphorus 9.7 0/0, chlorine 22.4 0/0. Example 12 A mixture of 47 g of 2: 4-dichlorophenoxyphosphoryl dichloride and 31.2 g of recrystallized colorless 4: 4-Dioxydiphenyl is heated exactly as in Example i i, but with 2 g of tin foil are added and the bath temperature for about 8 hours to igo to 195 ° is held. The resulting resin is a hard, tough and almost colorless body. After dissolving in gasoline, washing with ether and drying, its acid number is 9, and the softening temperature is 16o °.

Example 13 In a bottle equipped with a stirrer, 38.89 of hydroquinone, 500 cc of benzene and 56 g of pyridine are added. A solution of 74.5 g of 1'henoxyphosphoryl dichloride in 250 cc of gasoline is gradually added to the contents of the bottle with stirring and then stirred for 3 hours. A yellow-colored oily layer separates from the benzene. The contents of the bottle are then heated to 60 ° for 30 minutes with constant stirring. The heavy oil layer is separated from the benzene layer and then washed successively with benzene, water and ether and finally dried under reduced pressure. The resin obtained has similar properties to the product prepared according to Example i. However, it is a little darker in color and a little stickier.

All resins made according to the examples described are Soluble in chloroform and in benzene alcohol mixtures (80: 20% by volume). The optimal one However, the ratio of benzene to alcohol changes slightly for the different Resins.

The resins can also be dissolved in benzene or toluene to get concentrated To give solutions, which then with a benzene alcohol mixture to the desired Consistency to be diluted. It is advisable not to use a solution containing alcohol to be stored because this increases the acid number. The addition of alcohol should be take place before the solution is processed further. Certain resins of those described Art are also soluble in butyl acetate, ethyl acetate and acetone and produce clear ones Solutions. Other solvent mixtures that dissolve the resins described Mixtures of butyl or amyl acetate and aromatic can be used Hydrocarbons that contain small amounts of aliphatic alcohols, how they are used to dissolve nitrocellulose.

The resins can be rendered infusible by heating them in the presence of various metal oxides such as lead oxide. This also has the effect of reducing the solubility of the resins in organic solvents. If, for example, a small amount of such an oxide, for example 1 to 5% black lead, is incorporated into the plastics mentioned and then the product is baked at 80 to 200 ° for a certain time, the plastics become infusible as a result.

According to the invention from chlorinated or brominated aryloxyphosphoryl dichlorides Resin-like products produced have a greater hardness, higher softening temperature and a lower flammability than if made from non-chlorinated or not brominated aryloxyphosphoryl dichlorides getting produced. Farther it should be noted that the higher the chlorine or bromine content of these resins, the the more pronounced these properties are.

Claims (6)

PATENT APPLICATION :: _ i. Process for the production of resinous polyesters, characterized in that aryloxyphosphoryl dichloride and mono- or polyvalent aromatic dioxy compounds, the two hydroxyl groups of which are not adjacent Carbon atoms are, preferably with heating and / or in a neutral Atmosphere to be condensed. 2. The method according to claim i, characterized in that that as aryloxyphosphoryl dichloride phenoxyphosphoryl dichloride, p-chlorophenoxyphosphoryl dichloride or o-chlorophenoxyphosphoryl dichloride, such as. B. 2, 4-dichlorophenoxyphosphoryl dichloride, 2, 4, 6-trichlorophenoxyphosphoryl dichloride, 2, 4-dibromophenoxyphosphoryl dichloride, o-methylphenoxyphosphoryl dichloride and 2-methyl-4, 6-chlorophenoxyphosphoryl dichloride, be used. 3. The method according to claim i and 2, characterized in that Hydroquinone, resorcinol or dioxydiphenylene are used as aromatic dioxyver bonds will. 4. The method according to claim i to 3, characterized in that the aryloxyphosphoryl dichloride and the aromatic dioxy compounds are used in equimolecular proportions will. . Method according to Claims i to: 4, characterized in that after completion the condensation product is placed under vacuum. 6. Procedure according to claim i to 5, characterized in that the condensation takes place in the presence a catalyst supporting the formation of hydrogen chloride takes place. . procedure according to claims i to 6, characterized in that the catalysts used are metallic Tin, calcium chloride, boron trifluoride, zinc or aluminum chloride can be used. B. The method according to claim i to 6, characterized in that the condensation in the presence of a common solvent, such as. B. ether, benzene or chloroform, takes place, whereby in this solvent a substance absorbing hydrogen chloride, z. B. a tertiary amine, preferably pyridine, is included.