DE1570992A1 - Poly (phenylene oxides) and processes for their preparation - Google Patents

Description

15709 «

<■ ^{ίΑ c} j ^L

M I817

Minnesota Mining and Manufacturing Company, Saint Paul, Minnesota 55101, V.St.A.

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Poly (phenylene oxides) and processes for their preparation

The invention relates to polyphenylene oxide polymers and more particularly such polymers with improved properties. According to In one embodiment, the invention relates to a novel one Class of amorphous, soluble, low-melting, relative high molecular weight polymeric compounds. According to another embodiment, the invention relates to films made from these polymeric compounds and articles coated with these polymers. According to a further embodiment, a " Process for chain extension of certain soluble poly (phenylene oxides) suggested. 0ÖÖÖ1 2/1 002

Documents (Art? SI Abe.2 No.! $ Att3dMÄixJ * rung $) es.v.4. * 116a

BATH

on the production of poly (phenylene oxides) is of various kinds Page has been reported, see U.S. Patent No. 2,961,334, British Patent No. 930,993 and Soc. Chem. Ind. (London), Monograph No. 13, pp. 231-267. The after the However, the polymers produced by the processes described therein have one or more of the following disadvantages: (1) low molecular weight, (2) Inconsistency at high temperatures (especially prolonged exposure), (3) inability to form tough, pliable films and coatings, and / or (4) deficiencies Processability due to extensive unregulated crosslinking during the polymerization reaction. The applicability of this Substances is limited accordingly.

U.S. Patent No. 3,268,478 describes certain poly (phenylene oxides) in which the phenylene oxide repeating units are meta-oriented and which is disclosed
Properties that were previously not achievable, especially a «very
desired better heat resistance. The meta-oriented polymers do not, however, provide a satisfactory solution to the problem of how to obtain a high degree of temperature resistance (phenylene oxides), because the meta-halophenols from which they are made can only be made with great ease of a very good process
can and are therefore so expensive that the m-polymers,
in practical terms, cannot be used.

The invention is based on the object of a new « vmä.

QÖI & 12 / 1S02

to provide a bare class of polymers. The invention is also based on the task, a suitable class of To develop protective coatings. To further objects of the invention include developing new and useful polymeric films, a new class of heat resistant polymers, one new class of soluble polymers with relatively high molecular weight, which can be networked to form tough, flexible films and coatings, as well as a new class of Intermediate products for the manufacture of certain highly haf- |

protective coatings and finally a new class of intermediate products for the production of certain tough, infusible, inert molded polymeric objects.

There were now poly (phenylene oxides) with advantageous properties found the 45 to 75 mol # p-phenylene oxide units and contain o-phenylene oxide units as the remainder and

(1) a temperature for a 10 #igeri weight loss of about 500 ° C or above (according to thermogravimetric analysis - TGA-at a rate of temperature increase of 5 ° C per minute),

(2) Softening ranges below 150 ° C, determined by thermal Differential analysis (DTA),

(3) intrinsic viscosities, based on liquid solutions of the polymer in concentrated (98 #) sulfuric acid, of at least 0.3 and

(4) have practically complete solubility in benzene at 25 ^° C.

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The preferred polymers have molecular weights of 2,000 or more higher in order to achieve good mechanical properties (impact resistance, Elasticity, etc.). The p- and o-copolymers, which contain more than about 75 MoI-Jo p-phenylene oxides, tend to be incomplete (and are not completely amorphous). This is a disadvantage in processing and handling. On the other hand, similar copolymers tend to be less than about 45 mol- ^ p-PhenyJ enoxydeinhei th to it, for optimal ™ mechanical properties have too low a molecular weight. Although the pour points of the polymers according to the invention are relatively low, they can be implemented further and thereby inextensible through networking via their terminal groups and result in infusible materials. In this way it is possible to take advantage of the high heat resistance of the polymers to take advantage of.

As the TGA test values are generally related to the ability of polymers, with continued use at high temperatures To be stable, the high values of the polycondensates produced according to the invention are of great importance. Of the The test is described in the article "Thermogravimetry Measurements" by A.E. Newkirk, Analytical Chemistry £ 2, 1558 (1960), dicuted.

The DTA test is described in Chapter IX of the book "Newer Methods of Polymer Characterization "by Bacon Ke, Intersciense Publishers, New York, 1964.

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The polymers according to the invention are produced by polycondensation a monomer charge in the presence of a solvent and a catalyst (a soluble copper salt). More precisely, this is done by polymerizing a suitable one Mixture of p- and o-oriented potassium salts of monochlorophenols,

The percentage of p-phenylene oxide groups / _> / ^ \ -O- J and

o-phenylene oxide groups I 0 > \ -0- J in the polycondensation

product is roughly determined by the relative amounts of o- and p-monomers determined in the monomer feed,

The process used to manufacture the polycondensation products consists of the following individual stages:

(1) Production of alkali halogen phenolates from o- and p-chlorophenols, which contain practically no phenol or polychlorophenol, by neutralizing the chlorophenol with aqueous potassium hydroxide solution in the absence of oxygen or air with removal of the water;

(2) Purification of the potassium chlorophenolate by crystallization a non-aqueous solvent, the crystallized salts being less than about 0.05 # water (determined by Karl Fischer analysis ) contain; and

(5) Preparation of the polymer by introducing the monomer salts in the desired proportions, 0.01-1 mole # of a catalyst £ ~ a copper (I) - or copper (II) salt, such as

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■ BAD ORiGINAt

Copper (l) chloride, copper (II) chloride or copper (l) cyanide_7 and 2-100% by weight of pyridine or quinoline in a suitable reaction vessel in the absence of oxygen bz «. Air and heat of the mixture initially to around 100 - 175 ° C for around 2 - 24 Hours and finally to around 200 - 275 ° C for one or several hours.

If the final reaction temperatures are below 225 ° C, this usually leads to a reduced intrinsic viscosity, a lower average molecular weight (according to e.g. vapor pressure osmometry, ^ p ₀ ) and a lower ability to form tough, flexible films (e.g. determined by the Number of folds by lo0 ° that a film sample made from the polycondensation product survives and cured for 15 hours at 400 ° C with the aid of 5% dicumyl peroxide). It is often desirable to finally use reaction temperatures of 225 - 250 ° C in order to achieve the best intrinsic viscosity and the best average molecular weight.

According to another embodiment, the isomeric phenols are mixed together in the desired proportions before neutralization with potassium hydroxide and crystallization of the anhydrous salt of pyridine takes place.

The exclusion of impurities from the monomer starting material rial, the monomers and the polycondensation mixture (at least

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until the polycondensation is complete) and the introduction of various special ingredients at special times during of the whole process have opted for the process according to the invention proved essential. The following essential conditions apply »

1. The monomers must be at least about 98% pure Chlorophenol (excluding water) can be produced that practically no phenol or polychlorophenol (determined by gas chromatography ) contains.

2. Oxygen must come from both the chlorine and phenol the potassium hydroxide must be carefully removed before these substances mixed together to produce the monomer salt and must be continuously excluded during the manufacture, drying and storage of the salts. See this not, there is an extensive formation of color bodies in the solution instead, which are deposited on the otherwise colorless salt.

3. The monomer should not be more than about 0.05 # water

(determined by Karl Fischer analysis) included, since higher Percentages of water tend to be obtained Polymers have a lower molecular weight.

4. The polymerization charge must be about 0.01 - about 1 mol $ of a copper (I) or copper (XI) salt as a polymer tion catalyst included. Smaller amounts of catalyst are sufficient

^009012/1602

do not fail to effect the desired polymerization while higher catalyst concentrations lead to the formation of polymers with lower molecular weights.

5. Oxygen should be excluded from the polymerization mixture be, as its presence diminishes the

, Quality of polymer leads.

6. The Polymerisationsreaktionsgemiscn must be about 2 - 100 weight -.% Pyridine or quinoline included. If the reaction mixture does not contain pyridine or quinoline, soluble polymers of much lower molecular weight are formed which contain relatively large amounts of insoluble, crosslinked polymeric materials.

In the production of the polymers, it has proven to be advantageous that the first addition of catalyst takes place after the monomer salts have reached the 3ent temperature door of 150-160 ° C have, with more during the last stages of the polymerization Amounts of fresh catalyst are added. Furthermore, it has been found desirable in the final stages of the Add a diluent such as diphenyl ether to the polymerization, to lower the viscosity of the reaction system. This makes it possible to run the process at or near atmospheric pressure perform and reduce the reaction time. These conditions also result in a lighter colored product and often to a higher molecular weight.

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The linear (or practically linear) copolymers obtained in this polymerization process are completely soluble (even at room temperature) in a number of different solvents, are low-melting and amorphous (determined by X-ray diffraction diagrams of the finely powdered polycondensation products) and have relatively high molecular weights. The relatively high molecular weight of the soluble polymerization products is a prerequisite for the presence of strength and stability in these polymers, regardless of whether they are ultimately used without further modification (e.g. as soluble thermoplastic materials) or cured and crosslinked to form infusible, insoluble materials should. The relative molecular weights of these polymers can be conveniently tf / else from their intrinsic videos itätswerten in sulfuric ^e £ proceed. It has been found that polycondensation products which have intrinsic viscosities in sulfuric acid of about 0.15 or greater have useful strength, flexibility and toughness.

Usually soluble polycondensation products that are intrinsic Have viscosities of 0.3 or above at the above Polymerization process described obtained directly. If, however it is desired to increase the molecular weight (and intrinsic viscosity) of a polymer obtained by this process increase, so can the methods of fractionation or oxidative Chain extension can be applied. Fractionation

009812/1602 BADORLGiNAL

can be done in such a way that the polymer is in a solvent, such as benzene, toluene or methylene chloride, dissolved, the solution is filtered through diatomaceous earth to remove any gel constituents or inorganic compounds entrapped in the polymer To remove salts, and then falls by pouring into methanol. Affect the concentration of the polymer solution and the solvent to a certain extent the proportion of the removed low molecular weight Polymer and in this way the quality of what is obtained Polymers. In a typical experiment, the polymer dissolved in about 9 times the amount by weight of benzene and poured through the filtered solution is precipitated in 5 parts by volume of methanol. If the solution is added with only very weak stirring, the high polymer components fall in the form of rubber-like lumps down, while the low molecular weight fractions in the form of a

remain suspended in the benzo1-methanol solution. This The low molecular weight fraction can be removed by evaporation of the milky suspension to dryness, initially on a steam bath and finally under vacuum.

The insoluble, rubbery lumps consist of the polymer plasticized with benzene. The benzene can be removed by heating Vacuum (which is usually not recommended because the mass tends to be many times its original Volume) or removed by extraction with methanol and finally washing with methanol in a mixer will.

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The oxidative chain extension takes place under mild conditions carried out. It is easiest to do in the way that the polymer is dissolved in a solvent and treated with an oxidizing agent, such as one that is capable of converting phenolic groups into phenoxy groups. The chain extension appears to be due to the conversion of the free hydroxyl groups to take place in the polymer. Among the oxidizing agents used there are sodium hypochlorite, lead tetraacetate, Lead dioxide + alkali, potassium ferricide + oxygen, or copper (i) chloride + Oxygen at temperatures within the range from room temperature to 250 ° C. The extent of the chain extension is determined by the amount of oxidizing agent and the temperature. This procedure can be done in a convenient way too Apply the work-up of the polymer by using the solvent diluted, add copper (I) chloride and air for a long time Passes through the mixture at 50 ° C until the desired viscosity

is. ·

achieved wii? el ·. ·

The soluble polymers obtained by the process according to the invention are sometimes used directly, without modification to experience. More often, however, curing agents are incorporated into the polymers before they are put to their end use will. Among the useful hardening agents are peroxides such as dicumyl peroxide, di-ter.-butyl peroxide, benzoyl peroxide, Lauroylperoayd and other free radical generating compounds, such as azobisisobutyronitrile. The hardening or crosslinking can be usually bring to completion without heating. the

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fully cured polymers are generally characterized by being tough, strong, flexible, infusible, insoluble, chemically inert, resistant to hydrolysis and insensitive to heat are.

It is often also desirable to fill the resin compositions with fillers to be provided or stretched, e.g. by adding particulate or fibrous fillers such as calcium carbonate, Iron oxide, titanium dioxide, fuller's earth, quartz powder, asbestos, glass threads, etc., or in some other way the electrical, physical ones or chemical properties of the resin by incorporation of Plasticizers, dyes or pigments, other resins, conductive materials such as carbon or metal powders, etc., which are used as Additions can be viewed, and the like. Modify.

Among the other additives that make up the compositions according to the invention may be incorporated, there are solvents such as benzene, toluene and xylene, chlorinated solvents such as chloroform and methylene chloride, pyridine, tetrahydrofuran, dimethylformamide, Dioxyn, Whore thy Iac etamid, N-Methylpyrrolidon and D-i ph eny lather as well as high-boiling stable liquids such as liquids Polyphenylene oxides. These solvents or liquids can be used for diluting or stretching the masses. Antioxidants such as the symmetrical di-ß-naphthyl-p-phenylenediamines (under the trade name "Agerite White" from the R.T. Vanderbilt Company), certain liquids Level A phenol-formaldehyde resins (such as the liquid anti * Oxidizing agent "Stabilite White", a product of CP. Hall

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BATH ORIGINAL

Company, Akron, Ohio), di-o-toluylethylenediamine (under the Commercial name "Stabil! Te Alba" from the CP. flail company available), etc., can be the same as, if added.

The following examples serve to specifically illustrate preferred embodiments of the method according to the invention, however, without restricting the invention. Unless otherwise stated, all parts are parts by weight. In the examples, which deal with the production of the polymers, the softening areas were determined by thermal differential analysis (DTA) certainly. The intrinsic viscosities were at 2 ^ ° C below Use of a 1 $ solution of the respective polymer in concentrated Sulfuric acid obtained by heating the polymer and the acid together, e.g. 30 minutes at about 145 C is usually sufficient.

Preparation of the monomers

The structural formulas and the content of the crystalline salts of pyridine built into the crystals of the monomer preparations described below are as follows:

■■ -.-. BATH

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description

of the monomer

formula

Cl -

-OK

Crystallization pyridine (Moles per mole

Honomeres)

0.07

Preparation of the monomer A

000 g (k , 67 mol) of colorless p-chlorophenol are weighed into a 3 liter three-necked flask with 1400 ecm of analytically pure pyridine and 250 ecm of analytically pure benzol. The flask is on one side with a 3 cieks tof fine line tube and a drip funnel, in the Mi *; a thermometer reaching down into the liquid and a Barrett water separator on the other side, a small column filled with 3.2 mm Pyrex spirals being arranged between the flask and the Barrett water separator. About 550 g of an aqueous solution of potassium hydroxide containing a total of 4.33 mol of carbonate-free potassium hydroxide £ ~ Kolthoff, Zeitschr. anal. Chem. Öl, 43 (1922) _7, are weighed into the dropping funnel, and the whole apparatus is freed of oxygen by repeated evacuation and filling;: i with purified nitrogen. The solution is stirred with the aid of a magnetic stirrer and the potassium hydroxide solution is allowed to run into the flask. The solution will be

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BATH

heated to reflux .tempera door while a slow stream purified nitrogen is passed through the piston. That Water is removed rapidly, initially using a reflux rate equal to the capacity of the column is equivalent to. After oO - 90; ί the theoretical amount of water are removed, the boiling speed is reduced - by to achieve a separation which requires a number of hours. Overall, the reflux is heated 9'5 "- 163 hours or continued until no more Deposition on the aqueous phase can be determined. While during this period the temperature of the boiling liquid increases from 90 - 95 ° C to 110 -112 ° -C-, when the last water fractions removed. The removal of some of the benzene through the Barrett's water separator until the flask temperature II7 - 120 ° C is reached, the removal of the last traces of the aqueous phase facilitates. Then an additional 550 ecm of solvent .tel removed through the Barrett's water separator, which removes the Piston temperature rises to 124-126 C. The remaining hot, clear solution is obtained with the help of a glass transfer tube transferred into a filtering vessel by injecting nitrogen, the '"- is provided with a sintered glass pane at its bottom. The solution is allowed to cool in the filter vessel while Maintain a certain nitrogen pressure at the bottom of the vessel so that the solution does not run through the filter. White needles quickly form, and when the mixture has reached room temperature, a solid, white mass of salt has formed. The mother liquor is removed by injecting nitrogen

009812/16 02 ■ bad original

and the solid mass broken up and with the smallest possible Amount of a dry benzene-pyridine mixture (3: 1) washed. The solid mass is dried under nitrogen pressure until no more liquid comes through the filter, and then the solvent by evacuating for several hours Room temperature further away. A constant weight will be when the salt reaches 2 molecules of crystal pyridine per 3 molecules Contains potassium p-chlorophenolate. The salt mass is in one closed system in a dry nitrogen atmosphere mechanically shaken and sieved to break the large lumps into a fine, free-flowing powder.

Analysis for water using Karl Fischer reagent shows that the salt contains less than 0.03% by weight of water. The crystal pyridine can be easily removed by heating the salt in a vacuum on a steam bath. The salt freed from the solvent in this way has a neutralization equivalent weight (pH = 6.0) of 166.1-167.0 (theoretical value = 166.6) and melts with decomposition at 211-214 ° C. (evacuated capillary). Both with and without a crystal solvent, it is very hygroscopic and must be stored under nitrogen. The yield is 770 g, which corresponds to 77 % of the theoretical yield.

Production of the monomer B o-chlorophenol is used to remove traces of phenol, 2,4-di-

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Chlorophenol and p-chlorophenol contained in the commercial material are fractionated. Analysis of the colorless distillate by gas chromatography shows that the material has a purity of more than 99.9 % .

A solution of 1200 g of this material in -2400 ecm of pyridine (freshly distilled over barium oxide) and 600 ecm of analytically pure benzene is placed in a 5 liter three-necked flask equipped as in Example A (which describes the production of monomer A) , But does not have a thermometer. An adjusted 50 # aqueous, carbonate-free potassium hydroxide solution is added to the dropping funnel in an amount equal to 97% of the equivalent amount calculated on the phenol, and the whole system is evacuated and filled 10 to 12 times purged with high purity nitrogen. The aqueous potassium hydroxide solution is then added to the flask while the system is additionally flushed several times with nitrogen. It is stirred with the aid of a magnetic stirrer.

When all of the potassium hydroxide solution has been added, the dropping funnel is replaced by a thermometer that reaches below the liquid level and the solution is heated to reflux temperature. It is heated for about 2 days and the water is collected in the Barrett's water trap. It is then heated to reflux for a further 24 hours, after which the benzene and pyridine are removed by the Barrett separator until the temperature of the liquid has reached 126-128 ° C. '. _/ ----- ^ - ~ —__

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- 13 -

The solution obtained is then in a still hot state Injection of nitrogen into a closed filter vessel containing 25OO ecm of dry, analytically pure benzene. The product quickly crystallizes in the form of white granules that settle on the bottom of the funnel. After the mixture has cooled to room temperature, is the mother liquor is removed by injecting nitrogen and the remaining solid mass is washed once with dry benzene and dried by evacuation at 100.degree. The received solid Potassium o-chlorophenate weighs 6 "SH g (46 #) and contains 0.01 0.02 # Water as determined by analysis with Karl Fiscner reagent. The titration with adjusted hydrochloric acid up to pH = 6.0 results in a neutralization equivalent weight of 1-57 * 1ί the theoretical Value is Io 3.6.

Manufacture and testing of polymers example 1

This example illustrates the preparation of copolymers that have no subscriptions.

610.2 g (5 »065 mol) of the monomer B are transferred from a storage container through a thin-walled rubber hose into a 3-liter autoclave made of stainless steel which has been previously dried and purged with nitrogen at 200 ° C. Then be 14lo g (6.450 mol) of monomer A are added in the same way.

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Finally, 0.950 g (0.095 mol- ^) of purified copper (.I) chloride are added, and the adding device is replaced by the autoclave lid. The autoclave is then evacuated for several hours, filled with nitrogen, sealed and placed in a chute heater, where it is kept for 14 hours at 180 ° C and then for 5.5 hours at 250 ° C (3 hours are required to reach the respective temperature values necessary ). The autoclave is then cooled to 100 ° C. and 1 liter of methylene chloride is added to the charge, which is then ^{flushed from the autoclave with an additional 3} liter of methylene chloride.

The solution of the polymer is slowly added to 13.9 liters of methanol, which are fed with the aid of a Cowles dissolver. The solid mass obtained is filtered off, stirred with 4 η HCl and washed alternately with water and methanol (2 times and dried under high vacuum. The yield of tan-colored polymer is 896 g (90, ¹ * $). Intrinsic viscosity: 1 ^ solution in CHCl- = 0.263; 1 solution in concentrated H ₂ SO ₁ ^ = .0.513, the polymer has a softening range below lpO ° C and is soluble in benzene.

A thick-walled glass ampoule is dried in an oven and evacuated and filled with nitrogen while at room temperature is allowed to cool. 13, l3 g (Ο, ΟβΟΙ mol) of the monomer A and 6.74 g (0.04c4 mol) of the monomer B are then added directly to the vial weighed in, taking care that the salts so

00981 2 / 16Ö2 '■ "

PAD

come into contact with the atmosphere as little as possible. Then 10.6 mg (0.11 mol- #) of purified copper (II) chloride are added, and the vial is carefully evacuated to avoid drawing the solids into the vacuum line. The evacuation at room temperature and at a pressure of less than 1 mm Hg is continued for 16 hours before the ampoule (still under vacuum) is closed.

The contents of the ampoule are then mixed by shaking and the ampoule is first heated to 160 ° C for 10 hours and then to 250 ° C for 6 hours. The polymer is then isolated by treatment with 4η hydrochloric acid, followed by washing twice with water and twice with methanol, in a suitable mixing and milling apparatus (such as a Waring mixer). The tan powder yield is 8.78 g (94.5 %) . The intrinsic viscosity of the polymer, measured in sulfuric acid, is 0.394 g. In the thermal differential analysis, no sharp point of transition between different crystal structures can be found anywhere. However, a gradual endothermic effect is noted at around 73 ° C when the polymer first begins to soften. The polymer is soluble in benzene, toluene, chlorobenzene, pyridine, chloroform, methylene chloride and dimethylformamide at room temperature and insoluble in methanol, acetone and hexane *

A number of other copolymers of the invention other than Carrying subscriptions is done using the same

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manufactured »The manufacturing information and key figures of the products are summarized in the following table.

Feed (MoI- mono-
meres B. the end In tri ns is ehe mono-
meres A 25th prey
j> viscosity
in H ₂ SO ₄ 75 30th , 3 100 0.652 69.7 30th , 7 79 0.372 69.3 35 , 4 100 0.495 64.6 40 , 2 94.4 0.406 59.8 50 ,1 95 0.394 49.9 55 ,1 88.5 0.400 44.9 7Q, 8 0.316

Softening (C), bes t match by thermiscne differen tia la na ly se

135 105

135 '

<135 73

The polymers listed in the above table prove on rontgenographischer investigation as completely amorphous and are in all proportions at 25 ⁰ C in benzene, chloroform, toluene and chlorobenzene soluble, and the temperatures for a 10 #igen weight loss of the polymer in air (TGA -Temperature increase of 5 ° C per minute) are 500 ° C or more. ■ · .'.- ■■

The procedure of Example 2 below is to increase the Molecular weight of any particular polymer suitable, if such an increase is desired.

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BAD ORiGiNAL

Example 2

This example illustrates the increase in molecular weight of the polymers through oxidative chain extension.

A solution of 10 g mixed poly (p, o-phenylene oxide) (55 * 7 $ o-units, M " _w = 4000, ^ \ V = 0.257 in CHCl,), which has been prepared according to the general method of Example 1 , in 100 ecm of toluene is filtered and placed in a 200 cc column equipped with a magnetic stirrer, 25 ecm of aqueous 15% sodium hypochlorite solution are added, and the mixture is heated to 90 ° C. for one hour the reaction mixture is cooled and slowly added to 500 ecm of methanol with rapid stirring. The precipitated polymer is filtered off and washed with 5 HCl, water and methanol and then dried, 10 g (100 % yield) of a light yellow polymer being obtained; <f ^ J = 0.54 (1 % in chloroform), ff = 88ΟΟ. The product contains 1.0 % chlorine compared to the polymer used, which contains 0.4 % chlorine.

A solution of 50 mg of copper (I) chloride in 5 ecm of pyridine becomes a solution of 2.0 g of misehpoly (p, o-phenylene oxide) (55.7 % o-units, / 5h = 0.257.1 % in CHCl ₅ ) in 20 ecm of chlorobenzene. This mixture is heated to 50 ° C. while oxygen is passed through it at a rate of 1 liter / minute. After 1 hour, the mixture is cooled, quenched by pouring it into methanol and dissolved as described above.

009812Z ₁₆₀₂

is working. The polymer is recovered in quantitative yield and now has the following viscosity: = ■ Q * 75 (£ 1 in chloroform).

For both of these chain-extended polymers, the temperatures for a fig weight loss in air (TGA, temperature increase of 5 per minute) are 500 ° C or above, and these two chain-extended polymers have softening ranges below 150 ° C and intrinsic viscosities in sulfuric acid above 0.3 and are completely soluble in benzene at 25 ° _(C.

Example j?

This example illustrates the preparation of polymers where part of the catalyst to "start" to the molten monomer ren mix is given and then during the last stages further amounts of fresh catalyst are added to the polymerization, and during the last stages of the polymerization a diluent is added.

A 2 liter three neck "round bottom flask" is used, fitted with a ■ reflux condenser, - a stirring device with a stirring blade stainless steel, a thermometer and a nitrogen inlet tube is provided. The upper end of the cooler is connected to a template via a glass elbow, followed by a mercury trap to prevent oxygen or moisture from entering to prevent the system. The apparatus becomes thorough

O09Ä12 / 16O2

/ V BATH

flushed with nitrogen and then filled with 82J g (5.75 mol) of monomer A and 378 g (2.26 mol) of monomer B through a thin-walled rubber hose which connects the storage container to the apparatus. The flask is then heated using an electric heating mantle while a slow stream of nitrogen is passed through the system. The reaction mixture is melted at 160 ° C. At this point in time, a solution of 0.601 g of purified copper (I) chloride in 50 ecm of dry, rinsed pyridine is introduced through the nitrogen inlet tube with the aid of a subcutaneous syringe. The mixture is stirred and refluxed for J5 hours, after which the reaction temperature slowly climbs to 235 ° C., which requires 1-2 hours. A further 0.090 g of copper (I) chloride in 20 ecm of pyridine is then introduced and stirring is continued. When the viscosity increases, distilled diphenyl ether is added in 3 portions of 200 ecm each within 2 hours after the last addition of the catalyst. At this point the system is very viscous and must be diluted with 500 ecm of purged pyridine. The mixture is cooled and quenched by pouring it into methanol. Working up is carried out according to the procedure of Example 1. The yield of pale tan-colored, benzene-soluble polymer is 495 g (90 %). Intrinsic viscosity: 1% solution in CHCl, = 0.407

Solution in HgSO ^ = 0.420.

The softening of this polymer is below 150 ⁰ C, and its temperature for a 10 #igen weight loss in air (TGA, temperature rise of 5 ° C per minute) is 500 ° C or

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about that.

Example 4

This example explains the production of a copolymer of the invention without isolation of the monomer salt.

A 1-liter three-necked flask is used ;, the column with a packing, the upper at its end a Dean-Stark Azeotroptrenneinrichtung, and having an ^r n reflux condenser in the middle neck of the flask, further comprising a nitrogen-introducing tube and a thermometer on the one Stite and a dropping funnel on the other side is fitted. A Teflon coated magnet is placed in the flask and a magnetic stirrer is placed under the heating mantle that supports the flask.

Fyridine (230 ecm), benzene (130 ecm), p-chlorophenol (84.1 g, 0.654 mol) and ο-chlorophenol (45.3 g, 0.35 mol) are in the The flask entered through one of the side flask necks, and 45 # aqueous potassium hydroxide (123.8 g, 8.11 m VaI KOH per g, 1.004 moles) are added through the dropping funnel.

The upper part of the reflux cooler is connected to a vacuum line allied, and * the system is flushed several times with nitrogen, while allowing the base into the solution tiles within 5-10 minutes. The system will eventually run with nitrogen readjusted to atmospheric pressure and heated while maintaining a slight positive nitrogen pressure will.

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BATH

The water is removed by azeotropic distillation through the Dean-S tark attachment until no more water separates from the benzene distillate. At this point, the temperature of the solution in the flask is 120 - 125 ° C. The magnetic stirrer and the packed column are removed, a mechanical stirrer is placed in the middle neck of the flask, and the Dean-Stark attachment and the reflux condenser are inserted in place of the dropping funnel the lateral neck of the Kolberj arranged. The solvent is removed by the D .an-3tark add-on until the temperature of the solution reaches 1όΟ ° C. A solution of 1 mg CuCl in 10 ecm pyridine is added (conveniently by injection through the rubber tube of the nitrogen inlet line using a hypodermic syringe) and the temperature is set at 160-170 for 3.5 hours, if necessary by removing further solvent ° C held. Finally, the temperature is increased to 250 ° C. for 2 hours; 70 ecm of phenyl ether are added to the solution when the solution begins to thicken. The heat is then turned off, 80 ecm of pyridine is added, and the entire mixture, after cooling, is precipitated in methanol using a mixer or other high speed stirrer to disperse the solid polymer.

The slurry is filtered, and the solids are washed successively with water, methanol, dilute hydrochloric acid and finally with methanol before being dried in a vacuum oven at 50 ° C. The yield is

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ö'j, 2 g or 97 / »- ·. The polymer is soluble in many organic solvents such as benzene, toluene, pyridine, chloroform, chlorobenzene and tetrahydrofuran. The differential thermal analysis (DTA) shows that there is no crystalline melting point, and the thermogravinetric analysis (TGA) shows a 10 # weight loss at 500 ° C. The circular beam diffraction pattern of the solid is completely amorphous. The infrared spectrum of the polymer deposited on sodium chloride crystal from a chloroform solution shows no absorption for OH or aliphatic CH and is completely identical in structure to poly (p, o-phenylene oxide). The intrinsic viscosity of this polymer (in sulfuric acid) is greater than 0.3.

Example 5

This example explains the thermogravimetric analysis of the Polymers produced according to the invention.

The räerjaograviinetrisehen analysis (TGA) of different polymers obtained according to the invention, which are produced by the process of above examples are obtained as follows:

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BAD ORfGiNAL

polymer Loading in wt -.% Amount of
Monomer B TOA No. Amount of
Monomer in A 54.9
55.1
75.0 (Temperature, at
the 10 % weight
loss occurs,
in ⁰ C) 5a
5b -
5c 65.1
44.9
25.0 525
52β
520

Example 6

This example explains the use of the polymers produced according to the invention in the form of protective coatings and for Manufacture of linerless films.

1 g of a ρ, ο-PhenylenoxydcopoIy mers prepared according to the invention with 60 mol # p units and 40 mol # o units Z "" ^ *! ^ - 0.544 (in H ₂ SOj ₊ ) J is in 2.8 g Dissolved methylene chloride and 2.8 g of xylene, to which 0.05 g of tert-butyl peroxide are added, so that a 15 # solution is obtained which contains 5% by weight peroxide, based on the copolymer. The mixture is applied with the aid of a doctor blade in a layer thickness of 0.28 mm to a 0.25 mm thick aluminum foil and heated to 200 ° C. for about 16 hours. The hardened coating is tough, adherent and resists infiltration and detachment by corrosive agents.

An aluminum foil coated in this way is shaped an X-pattern is scratched, and a drop of koiizentrler-

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added hydrochloric acid to the center of the X. The aluminum will Etched through, but no hydrochloric acid penetrates under the film. Another sample of coated aluminum foil is sharp with a Ballighhammer struck, creating an impression of 5 mm. Concentrated HCl exposed to this impression yields within several hours no reaction, which shows that in the film have not formed any cracks. So the film is tough and can do without it Breakage or crack formation are deformed.

If the aluminum is removed with the help of concentrated hydrochloric acid, it becomes an excellent, smooth, clear, tough, pliable one Film received.

Based on other polymers used in the previous Examples have been described, or of others according to the invention Preparable polymers can be prepared in the manner described here using the various th peroxide catalysts as well as other compounds which produce free radicals and other additives, further compounds can be produced. The received Masses can be applied to metals, ceramic products, glass, plastics, filled plastics, layer structures, etc. and cured in the manner described herein, with lower temperatures and for less heat resistant materials longer curing times can be used. In this way, tough, flexible, firmly adhering, insoluble coatings are obtained. the Polymers can therefore be used in the production of chemicals and solvents! Coatings on a large number of the

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the most diverse support materials can be used.

The polymers can be in the form of hot melts, in the form of
Plastisol masses as well as being handled in the form of solutions in organic solvents. They are used as adhesives, sealing
or sealants, can be used as resins for the production of sealants and for laminating, for the production of moldings and - as already described above - for the production of coatings.

- patent claims -

009812/1602

Claims (1)

Patent claims: 1. Amorphous unsubstituted poly-xphenylene oxide) with about 45 to 75 mol # p-phenylene oxide units, the remainder being o-phenylene oxide units are and the polymer (1) a temperature for 10 # weight loss in air (determined by thermogravimetric analysis at a rate of temperature rise of 5 ° C per minute) of about 500 ° C or above, (2) a softening range below 150 ° C through thermal differential analysis, (3) an intrinsic viscosity as measured by a 1 # Solution of the polymer in concentrated (98 #) sulfuric acid of at least 0j3 and (4) Virtually complete solubility in benzene at 25 ° G having. 2 «polymer according to claim 1, characterized in that it contains about 65 MoI- ^ p- and ettia 35 MoI- ^ o-phenylene oxide units * ■ Unferiaeen mn \ Abe.2Nr.i sentence β «h. AKhTWe ₈ Be ₈ -V. 4, ». ims 009812/1602 BATH ORIGINAL ~ 5. Process for the production of amorphous poly (phenylene oxide) with about 45 to 7 ^ MoI- 'p-phenylene oxide units, the remainder being o-phenylene oxide units and the polymer (1) a temperature for a 10 ^ i ^ eη weight loss in air (determined by thermocravimetric analysis at a temperature increase of ^ ° C per minute) of about [j00 °. C or about that, (2) eiriin Krwelchungsbereicn I5O below ⁰ C, as determined durc.i differential thermal analysis, (j5) an intrinsic viscosity, measured on the basis of a 15% solution of the poly: ^v ; f ~ ren in concentrated (3%) sulfuric acid of at least 0.5 and (4) practically complete solubility in benzene at 2 ^ ° C has, characterized in that an amorphous poly (phenylene oxide) with lower molecular weight exposure of oxygen or sodium hypochlorite under mild conditions subject. 009812/1 6 U 2