DE1301129B - Process for the production of thermoplastic, aromatic polyether - Google Patents

Description

From US Pat. No. 2,506,486 it is known how thermosetting resins are made from a bivalent Phenol and a diglycidyl ether of a dihydric phenol. The reaction is favored by gentle heating or the use of catalysts and gives a gel and then a hard, infusible, crosslinked resin.

Insoluble hardened masses are produced by heating bisphenols and diglycidyl ethers in a molar ratio of 0.2 to 1 in the presence of alkaline catalysts which remain in the hardened end product and in all intermediate products. According to Example 3, diphenylolpropane and diglycidyl ether in a solvent mixture of equal parts of alcohol, acetone and toluene for 2 hours at 6O ⁰ C with potassium hydroxide as a catalyst in ratios of 1.1: 1, 0.95: 1 and 0.95: 1 mol Diphenylolpropane condensed to diglycidyl ether. However, the known reaction products and those of the present invention are completely different due to the use of completely different reaction conditions.

The manufacture of thermoplastic materials is nowhere described.

The manufacture of fiber-forming thermoplastics by condensing epichlorohydrin and phenolic dihydroxy compounds are described in U.S. Patent No. 2,602,075. The process can be carried out in one or two stages. Here are the Reactants either alone or in the presence of a diluent, generally Alcohol, and a large amount of water, causing the resin to precipitate. The one made in this way Product is suitable for drawing fibers. Due to the manufacturing conditions the resins are largely branched. Although some resemblance between some Process steps according to US Pat. No. 2,602076 and the present invention, it has been found that the resins of the above patent do not have the high impact resistance if they are in the form of pressed or otherwise shaped parts, as exhibited by the resins prepared according to the invention.

The invention relates to a process for the production of thermoplastic, aromatic polyethers by condensation of diphenylolalkanes with their diglycidyl ethers in the presence of a solvent and an alkaline catalyst at elevated temperature, characterized in that is that you 2,2-bis (p-hydroxyphenyl propane or 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 2,2 - bis - (3,5 - dichloro-4-hydroxyphenyl) - propane with a diglycidyl ether of the bisphenol used in a molar ratio corresponding to 0.98 to 1.025 epoxy groups per phenolic hydroxyl group, dissolved in such ketones, chlorinated hydrocarbons or ethers that dissolve both the reactants and the resulting polyether, or in Cyclotetramethylene sulfone, the solution being 20 to 60 percent by weight of the reactants and contains less than 1% water, reacts at temperatures of 75 to 150 ° C until the viscosity number of the polyether is at least 0.3 dl / g (measured at 25 ° C in dimethoxyethane), and then the Catalyst neutralized and / or removed by treating the solution with water.

This gives plastics which are distinguished by high impact resistance when they are in the form of molded, extruded or otherwise molded pieces, and the polycarbonates are similar in a number of properties and superior in some properties. The from according to the invention Moldings obtained from resins produced have excellent resistance to many chemicals, flow easily under injection molding conditions and are therefore suitable for injection molding and extrusion.

The polyethers produced according to the invention can also be produced without any chemical modification suitable for surface coatings that have excellent coating and adhesion properties own. Solutions of these plastics

Ao provided coatings show exceptional toughness, adhesion, abrasion resistance, hardness, flexibility and chemical resistance. Because of their excellent adhesion to various fabrics these plastics continue to be used as

as adhesives.

Particularly preferred are polyethers which are obtained by reacting 2,2-bis- (p-hydroxyphenyl) -propane (p, p'-bisphenol A) be made with its diglycidyl ether.

The bisphenol used in the process according to the invention can be essentially 100% pure or pure be a technical product with a slightly lower purity. Concentrates of bisphenols can be used will.

The second component in the process according to the invention, the diglycidyl ether of bisphenol, is a compound with two 1,2-epoxy groups in the end position in the molecule. The diglycidyl ether is used the same phenol used as the first reactant.

When carrying out the process of the invention, the epoxy component can be a pure one Diepoxide or a raw mixture containing a substantial amount of diepoxide. However, it is It is important that the raw mixture is free from monoepoxide and monohydric alcohol or phenol. It it has been found that e.g. B. with respect to pure diglycidyl ethers almost equivalent results the properties of the resins obtained can in many cases be obtained if one a crude mixture of diglycidyl ether of bisphenol, but without monoepoxide, monohydric phenol or monohydric alcohol used, e.g. B. a technical diglycidyl ether of diphenylolpropane, a viscous liquid with an average molecular weight of about 350 and one Epoxy value of 0.50 epoxy equivalents / 100 g ("Polyether A" of the USA patent specification 2,633,458). Other diepoxides that can be used are higher molecular weight diglycidyl ethers of bisphenol A, as described by Reaction of bisphenol A with epichlorohydrin in the presence of a basic compound with epichlorohydrin bisphenol A ratios from substantially below 5: 1, e.g. B. up to 1.45: 1 will; Such a diglycidyl ether of bisphenol A having a melting point is particularly preferred of about 70 ° C (determined by the Durrans-Mercury method in Gardner and Sward

3 4

"Paint Testing Manual", 12th edition, 1962, p. 367), mixture. Is the original concentration high

an average molecular weight of un- so it is generally necessary to add additional

risk of 900 and an epoxy value of approximately solvent in the course of the reaction to reduce

0.20 equivalents / 100 g. change the viscosity of the mixture and

In the preparation of the condensation product 5 solution holding of the product is added. It may from the bisphenol and its diglycidyl ether does not have to be significantly related to epoxy or phenolic a basic condensation catalyst are present, hydroxyl groups react. Water and alcohol z. B. as a concentrated aqueous solution of sodium z. B. tend to be with the respondents too or potassium hydroxide, as aqueous ammonia or react and are therefore not used as solvents suitable as the sodium or ammonium salt of a phenol, io. After all, it should be easy and complete z. B. the same dihydric phenol that can be removed as a reac- from the final reaction mixture to tion participant is used. Solid salts will make the recovery essentially complete dissolved in the reaction mixture. To enable aqueous solutions of solvent-free resin. The should be as concentrated as possible. Desired high impact strength is a property

The concentration of the catalyst during the 15 that the complete removal of the solvent

Condensation reaction must be at a very low level, especially during manufacture

of polymers for use in molding,

branched polymers of low impact strength extrusion and the like.

posed. It was found, however, that the reactivity in the manufacture of products for upper

speed proportional to the cat ao surface coatings, the product can after the neutralization

lyser concentration increase. The useful Besation of the catalyst dissolved in the solvent

rich the catalyst concentration lies between stay. The boiling point of the solvent must be

0.005 and 0.1 moles per mole of bis-contained such that the reaction at 75 to 150 ° C at

phenols. To get the best results, use a specific pressure that can be performed

det a concentration of preferably 0.01 as The solvent can be a mixture of individual

to 0.025 moles per mole. There may be compounds.

some catalyst with the impurities of the appropriate solution reactant meeting these criteria reacted. This results in a mediation are z. B. certain ketones, chlorinated carbon reduction the reaction rate and can be hydrogen and ether. Methyl ethyl ketone is a end the reaction prematurely. Is there a preferred solvent? Methyl isobutyl ketone, tere amount of catalyst is added, the reaction can be cyclohexanone, mesityloxide and other ketones, to be continued. It was found that chloroform, 1,2-dichloroethane and others were chlorinated basic catalyst with saponifiable chlorine rea- hydrocarbons can be used, insgiert, when the latter in diglycidyl ether is especially mixed with ketones, ethers such as dihanden is. It is therefore advisable to keep oxane, tetrahydrofuran, dimethoxyethane and hold down the reaction rate at the beginning rige alkyl (methyl or ethyl) ethers of ethylenein Add an extra amount of catalyst; the glycol alone is suitable in the mixture. Even enough to react with this chlorine. Cyclotetramethylene sulfone is suitable.

The water content of the reaction mixture is preferably adjusted to a desired value

tion mixture kept as low as possible, pre-reaction temperature, suitably between 75

preferably below 0.12 percent by weight. In each and 150 ° C, preferably in a range of 85

Trap, the water content must be kept as low as 120 ° C, brought and stirred on this

be that it does not hold 1 percent by weight over-temperature. The viscosity of the reaction

strides. Mixing is continuous or in time segments

Careful control of the ratio of 45 measured and the response interrupted when the dihydric phenol and diglycidyl ether of the two-indicating viscosity of the entire reaction mixture valent phenol in the reaction mixture is of that the condensation product has a viscosity number of the utmost importance in order to obtain a product with the ge in the range of 0.3 to about 1 dl / g, measured in to obtain the desired properties. Tech-Dimethoxyethane at 25 ° C has. Is the Annische Types of one or more reactants- 50 catch concentration of the reactants relative used, the correct ratio will be high, e.g. B. between 40 and 50 percent by weight, obtained by taking the epoxy equivalency and then adding small amounts of additional phenolic solution Hydroxy equivalency of the reaction partial agents can be added in the course of the reaction in order to Determined taker and reaction with a mi to prevent the solution from becoming overly viscous conducts research that becomes not less than 0.98 and 55.

no more than 1,025 vicinal epoxy groups per phe- After the reaction has been interrupted,

contains nolic hydroxyl group. The best result is the catalyst, preferably by adding it

nits are obtained with molar ratios corresponding to at least sufficient carbon dioxide, neutral

0.999 to 1.005 epoxy groups per hydroxyl group, sated. The reaction mixture is then added

preferably exactly 1.0: 1.0. A slight excess of 60 would be of solvent such as dioxane or methyl

on epoxy groups is a very little excess ethyl ketone, saturated with water in a suitable manner

preferred shot of phenolic hydroxyl groups. diluted, e.g. B. to 20 percent by weight reaction

The solvent should be capable of the reaction participants + product.

participants and the reaction products in reac- It was found that methyl ethyl ketone, the

tion temperatures in used concentrations 65 is a preferred solvent, a special one

get in solution. These concentrations have solubility for resins obtained according to the invention.

between 20 and 60 percent by weight, preferably a solution of 30 or more percent resin

between 35 and 45% of the total reaction is from a single phase at temperatures in

the area where washing and recovery are carried out. The addition of more Methyl ethyl ketone to reduce the resin content of the solution to 20 percent by weight causes a Separation into two phases, one mainly methyl ethyl ketone and the other mainly Contains resin. For this reason it is necessary to dilute the reaction solution as required with a better solvent for the resin, e.g. B. dioxane to perform.

When adding 1 to 3 percent by weight of water to that for diluting the resin solution The methyl ethyl ketone used surprisingly remains the resulting amount as the only liquid

Chemical Examination of Paints, Varnishes, Lacquers and Colors by Gardner and Sward, 11th Edition, 1950, p. 173 ff., And according to the Izod impact strength (ASTM D-256) notched and unnotched [cf. American Standard Methods, Part 27 (1964), Pp. 98 to 105].

Tensile properties including elongation according to ASTM D-638 [Part 27 (1964), p. 207], the Rockwell hardness according to ίο ASTM D-785 [Part 27 (1964), p. 306], the heat distortion temperature according to ASTMD-648 [Feil 27 (1964), p. 229], the bending properties ASTM D-790 [Part 27 (1964), p. 313] and the dielectric properties according to ASTM D-150

Phase. It can be determined in the same way 15 [Part 27 (1964), p. 22], works like a methyl ethyl ketone dioxane The viscosity number was in dimethoxyethane

Solution.

The reaction mixture can then be cooled and washed with enough water to at least to remove most of the salt formed during the catalyst neutralization. the Washing at this stage is not essential if the resin subsequently precipitates

25 ° C and given in dl / g. Values from 0.4 to 1.1 correspond to molecular weights of a little over 100,000 to 1,000,000.

The invention is illustrated by the following examples:

example 1

in one

large volume of water is obtained. Dissolves this in a kettle containing methyl ethyl ketone

precipitating solvent the salt from the catalyst is essentially 100% pure ρ, ρ'-bisphenol A,

Satorneutralisierung not or will be a different substance essentially 100% pure diglycidyl ether and

recovery method applied, then the resin must be a 60% aqueous solution of benzyltrimethyl-

solution at this stage should be washed to ammonium hydroxide in a molar ratio of

essentially removing the catalyst. 1.0: 1.0: 0.02 added. The mixture will be on

To obtain the 30 produced according to the invention, a content of 67 percent by weight of effective

Resin, the solution of the reaction products is adjusted before reactants. The solution will be

preferably to a resin content of about 20 Ge then heated to boiling temperature with stirring and

adjusted weight percent and the solution in thin at this temperature of about 80 ° C for 13 hours

Electricity kept cold in a strongly moving large volume. Then chloroform is in

Water poured in gradually and then the resin 35 was added in such an amount that the con

obtained in the form of schnitzel, e.g. B. by filtration, and dried. This procedure must the original solvent will be soluble in water. Instead of water, another liquid

concentration of the reactants (including reaction product) decreased to 57 percent by weight. After a total of 28 hours, additional chloroform is added in an amount that will suffice

can be used in which the resin is insoluble, 40 concentration of reactants to 50 Geaber the original solvent is completely lowered by weight percent.

is soluble. After a total reaction time of 57 hours

In a variant, the resin solution is poured after the solution is cooled, the same Voder Neutralization is added to the upper roller of a two-lumen chloroform and the resulting roller mill. The solution flows between the rollers 45 solution washed twice with amounts of water that through, and the solvent will quickly be out of the equal to the volume of the resin solution. The resin preserved thin film evaporated. The resin will then be phase rich in a vacuum oven obtained as a film free of solvents. 160 ° C and 50 mm Hg stabilized for 6 hours.

Other methods can also be used. The stabilized resin is then converted into dioxane

the neutralized resin solution as one 50 of a solution with a resin content of approximately thin body, e.g. B. solved with a thickness of no more 15 0/0. The solution is left as a fine

Pour current into ten times its volume of cold water (0 to 15 ° C) with vigorous stirring. The dioxane then dissolves from the resin solution in the aqueous phase, and this is obtained essentially solvent-free resin as a suspension of chips or fibers. The resin is recovered by filtration and resuspended in an amount of cold water that

It is of course also possible that 60 is approximately the same as that of the previous one Use of the Pro stage prepared according to the invention used. The washed schnitzel will be

than about 6.35 mm, is introduced into a flowing medium into which the solvent enters at a faster rate Speed can diffuse while the resin is insoluble in it.

In the preparation of resins for surface coatings, the reaction mixture becomes preferred washed with water in order to remove the salts formed in the catalyst neutralization.

products for surface coatings to win the plastic as a solid in the manner described above and then redissolving the solid to obtain the desired coating solution.

An excellent feature of the moldings produced from the plastics obtained is that high impact strength, measured according to »Physical and

recovered by filtration and dried in a vacuum oven.

The shredded resin produced in this way has a softening range of 145 to 185 ° C and a viscosity number of 0.35 to 0.45 dl / g. Discs have an impact resistance of 84.3 cm x kg (Gardner).

Example 2 ^ aIt of phenolic hydroxyl groups of the bis

phenols and epoxy groups of the ether is like

The thermoplastic material is determined from a usual. The reaction mixture will be like this Equimolar mixture of the two components adjusted in until they are equivalent in functional terms a modification of Example 1, with 5 epoxy being an equivalent to functional contains the monosodium salt of ρ, ρ'-bisphenol A in a phenol, the latter being the concentration in the kata includes the amount of phenol present in an amount of 0.02 moles per mole of bisphenol analyzer. Of the is used as a catalyst. The catalyst used is 0.05 mole of a monosodium amount free bis-phenol A is therefore 0.98 mole of salt of ρ, ρ'-bisphenol A per mole of bisphenol in per mole of diglycidyl ether. The reactants io the reaction mixture. The entire reaction is dissolved in methyl ethyl ketone to form a solution, participants are in a concentration of 40 Gedie 40 percent by weight of reactants by weight percent in methyl ethyl ketone. The Reak contains. The reaction is at 80 ° C with stirring tion temperature is 78 ° C and the reaction time Performed 108 hours. Corresponding to the working 72 hours. The plastic is made by thinning As in Example 1, the washing, the sta- 15 of the reaction mixture are of the same weight bilization, shredding and drying with dioxane and pouring the solution under vigorous performed except that acetic acid was stirred into ten times the volume of ice water, rend the water washing of the resin solution added a certain excess of acetic acid will. For each mole of sodium ion present, 1 mole is required to neutralize the catalyst Acid added. Contains 20 amount, won.

Softening range 255 to 310 ° C; Viscosity compression molded test discs of the corresponding

number 0.85 to 1.2 dl / g. Maximum impact strength of the resin produced in this example is 184.3 cm · kg (Gardner) on molded bodies. Chemical resistance tested. It was found that upon exposure to these disks, ver Comparative Example _{2 £} . _sc hiedenen liquids at 100 ° C for 24 hours, no

In the implementation form corresponding to chemical degradation with water, 5- and 25% game 2 with a ratio of 1.05 mol diglycidyl aqueous sulfuric acid, 5- and 25% aqueous ether of bisphenol A per 1.00 bisphenol A (a sodium hydroxide, 5% aqueous acetic acid, finally the bisphenol in the catalyst) a 25% aqueous sodium chloride and 5% gel is obtained, which takes place by reaction of the epoxy groups 30 sodium methoxide and methanol,
with the alcoholic groups of the chain instead of a _B. ·, ^

linear resin is formed. Examples

Using a ratio of one sets pure diglycidyl ether of p, p'-bis-

1.05 moles of bisphenol per mole of diglycidyl ether of phenol A and pure ρ, ρ'-bisphenol A with a di-bisphenol a resin with a 35 epoxy to total phenol molar ratio of 1.0: 1.0 is according to Example 2 significantly lower molecular weight than otherwise using 0.013 moles of monosodium salt and with an unsatisfactory impact strength of bisphenol per mole of bisphenol A µm. The Reaker hold. Participants are treated in dimethoxyethane to 40

If 1 3 weight percent solids are dissolved. The water concentration

"40 tration in the solution is 0.03 percent by weight.

The thermoplastic material according to Example 1 The reaction is carried out under reflux for 17.5 hours from equimolar amounts of pure ρ, ρ-bis-, the resin then having a viscosity phenol A and its pure diglycidyl ethers of 0.55 dl / g . The concentrated reaction mixture in the presence of potassium hydroxide is now diluted to about 20 percent by weight aqueous solution in an amount equivalent to 0.044 mol 45 by adding dimethoxyethane. The KOH produced per mole of bisphenol A. The reac attempt is ended after a further 11 hours, when participants are dissolved in methyl ethyl ketone to a flattening of the time viscosity curve of the solution 37.8% solution. The reaction is indicated at indicating that the reaction rate is carried out very 5.1 atm at 140 ° C for 1.5 hours. Wah- has become low.
At the end of the reaction or before the wash, no 50 -. . ,,.

additional solvent added. The Reak Comparative Example

tion mixture is in a mixture of water, The procedure of Example 5 is repeated using

Washed methyl ethyl ketone and CO ₂ , CO _{2 with} the exception that the water content of the reac is present in a sufficient amount to neutralize the catalyst mixture from 0.03 to 1.0 percent by weight of the analyzer. The mixture becomes stable- 55 is increased. This increase in the water content siert, the stabilized resin dissolved in dioxane and this results in a tenfold increase in the alpha resin chips, as in Example 1, obtained. Maximum glycol formation, with the greater part of the increase in the impact strength of the molded bodies 184.3 cm · kg taking place in the first 12 hours of the reaction. (Gardner); Softening interval from 145 to above. Under the reaction conditions the alpha-glycol group at the end of 150 ° C. reacts very slowly, if at all, with a functional epoxy group;

therefore, glycol acts as a chain terminator. the

It will be technical bisphenol A with about the speed of disappearance of the funk-96.5 ° / o ρ, ρ'-bisphenol A and a commercially available ionic phenolic hydroxyl group in the Reaction product of the same type of bisphenol A 65 containing 1% water system is only half with epichlorohydrin with about 70 to 80% pure to a third of that of the reaction, the 0.3 Ge diglycidyl ether of ρ, ρ'-bisphenol A and the remainder weight percent water. From these results higher reaction products are used. The conscience clearly shows that increasing the

Water content of the reaction system not only changes the achievable final molecular weights of the resin, but also noticeably slows down the reaction rate.

Example 6

By adding sufficiently pure ρ, ρ'-bisphenol A and diglycidyl ether of ρ, ρ'-bisphenol A. to methyl ethyl ketone in a corrosion-resistant steel container is a 40 weight percent Solution of reactants prepared, the ratio of reactants being 1.0: 1.0 Epoxy to phenolic epoxy equivalence. The catalyst is 0.02 mol per sodium hydroxide Moles of bisphenol A, as a 45 weight percent solution. The reaction is carried out at 120 ° C and terminated by adding an excess of CO after a viscosity number of 0.34 or 0.37 dl / g has been obtained. The crude product solution is twice with half the volume of methyl ethyl ketone, saturated with water, washed to keep the sodium hydroxide content of the resin below 0.1 milliequivalent per 100 g of resin to decrease. The resin is removed from the solution by precipitation with cold Water obtained with vigorous stirring.

According to the invention
manufactured
Polyether span Poly
carbonate not free of charge not span made span free of charge at 71 ° C free of charge made made Dielectric con 4.00 stante, ΙΟ ³ Hertz ... 4.07 3.02 Power factor, 0.16 103 Hertz,% 0.19 0.11 Specific cons 3.69 stood, Ω · cm · 10 «.. 4.88 2.1

Example 7

Viscosity number

Epoxy, eq / 100 g

Phenolic hydroxyl,
Eq / 100 g

Alkalinity, eq / 100 g

Secondary hydroxyl,
Eq / 100 g

Methyl ethyl ketone,
Weight percent

Water, percent by weight

Chlorine, total weight percent

Inorganic chlorides,
Weight percent

Ash, percent by weight

Heat distortion temperature
[17.9 cm / ° C (ASTM D-648)]

Vicat softening point, ° C
[ASTM TeU 27 (1964), p. 229]

Notched impact strength, Izod,
(Average) kg · cm / mm notch

Unnotched impact resistance,
Izod, kg cm / cm ^s (average)

Resin bath

No. I.

0.37 0.0051

0.012 0.04

0.331

0.08

0.8

0.03

0.0035 0.02

89

100.2 0.63

6.5

Harz bath no.2

0.34 0.0053

0.011 0.04

0.332

0.08

0.5

0.02

0.0014 0.01

86

96.5 0.67

7.0

The flow properties of the samples in injection molding are satisfactory. On the other hand, it was found that a commercially available polycarbonate causes extremely great difficulties in molding, even at an injection pressure of 1360 atm and a cylinder temperature of 315 ° C. It has been observed that signs occur at dusk, when the polycarbonate is molded at this temperature using cycle times of 3 to 5 minutes, while no signs be noted at nightfall a polyether prepared in accordance with the invention during the molding at 31o ⁰ C.

In a boiler containing methyl ethyl ketone, technical bisphenol A (p, p 'content 96.5%)

ao and a solid diglycidyl ether of bisphenol A (Durrans mercury melting point of about 70 ⁰ C, molecular weight about 900, epoxy content approximately 0.2 ÄquivaIente / (100 g) in a ratio of 1.01 epoxy groups per phenolic hydroxyl group

as dissolved to a 40 weight percent solution; 0.15 percent by weight of sodium hydroxide, calculated on the total amount of reactants, was added as a catalyst in the form of a 45% solution in water. The solution was ^{heated at 130 °} C. for 6 hours, cooled and neutralized by adding gaseous carbon dioxide. The solution was brought to a resin content of 20 percent by weight with methyl ethyl ketone and washed with water. The solid resin was recovered by pouring the solution washed (1 part by volume) in 10 parts by volume of ice water with vigorous stirring, washing the resin with water scavenger, and dried at 100 ⁰ C (16 hours).

The resin had a viscosity number of 0.39 dl / g, a softening point (Vicat) of 100 ^° C .; Discs withstood an impact of 184.3 cm · kg (Gardner) without breaking or cracking.

Example 8

From a mixture of 925 g of epichlorohydrin (10 mol) and 284 g of 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane (1 mol) and 240 g of 33% sodium hydroxide solution (2 mol) is the diglycidyl ether in Obtained in the form of a practically colorless liquid containing one epoxy equivalent per 230 g.

284 g of 2,2 - bis - (3,5 - dimethyl - 4 - hydroxyphenol) propane (1 mol), 460 g of diglycidyl ether prepared as above (1 mol, calculated on the epoxy equivalent) and 3.28 g of the disodium salt of 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane (0.01 mol) are dissolved in 1500 g of cyclotetramethylene sulfone. The solution is kept at 140 ° C. for 6 hours. the Polymerization is terminated by adding a small amount of bis- (3,5-dimethyl-4-hydroxyphenyl) propane admits.

The reaction liquid is then mixed with 6.0 kg of dimethylformamide. The diluted solution is poured into water to which 0.05% hydrochloric acid has been added. The polymer is precipitated in the form of white flakes which are removed by suction, washed with water and dried at 120 ⁰ C. The viscosity number in dimethylformamide is 0.56 dl / g.

Claims (1)

11 12 From this polymer through compression molding at. The polymerization time is 10 hours. 250 ⁰ C test plates prepared following the viscosity of the polymer is 0.53; there- Properties: test plates made from have a very good _. , "" "" _,. "" Rings moisture absorption and good mechanical Softening temperature 123 ° C at 0.1 mm ₅ properties (Vicat) 128 ° C at 1mm ^B Yield strength 633 kg / cm ² Claim: Elongation at yield stress 10 · /. Process for the production of thermoplastic, Impact strength. .. 210 kg / cm * aromatic polyether by condensation of £ S u ™ hmebei 23 ° C '' ^ "D ^ nylolalkanes with their diglycidyl ethers in Weight gain in C Zi presence of a solvent and an al- w ater kaiischen catalyst at elevated temperature, Ä ~ Tip ^! F the water ¹⁵ dimethyl-4-hydroxyphenyl) propane or 2,2-bis- for 3 hours .... 1.50 percent by weight g of ₅ 5-dichloro-4.hydrox _y ph _e nyl) propane with a for 5 hours .... 1.65 percent by weight gSSFiST Χ ^ Χ ^ Γΐ, Μ Example 9 epoxy groups per phenolic hydroxyl group, ^v ao dissolved in such ketones, chlorinated coal from 366 g 2,2-bis (3,5-di-chloro-4-hydroxyphenyl) - hydrocarbons or ethers containing both the Reakpropan (1 Mol) and 925 g of epichlorohydrin is a participant as well as the resulting poly-diglycidyl ether, dissolve in the form of a solid white ether or in cyclotetramethylene sulfone, ßen substance with a melting point of 78 ° C, the solution being 20 to 60 percent by weight of the one Contains epoxy equivalent per 249 g (theory: as reactants and less than 1% Was-1 epoxy equivalent per 239 g). contains water, at temperatures from 75 to 150 ⁰ C The polymerization of this diglycidyl ether (1 mol, converts until the viscosity number of the polyether calculated as twice the equivalent weight) at least 0.3 dl / g (measured at 25 ° C in Dimit the corresponding Bis- (dichloro) -phenol (1 mol), methoxyethane), and then the catalyst from which it has been prepared is neutralized as for 30 sator and / or by treating the bis (dimethyl) derivative according to Example 8 by- the solution removed with water.