DE1769417C3 - Process for the production of hardened moldings from synthetic resin - Google Patents

Description

special chloroform or trichlorethylene, which are otherwise difficult to treat (insoluble) and

finds a turning point. infusible high polymer polyphenylenes can

5. The method according to one of the preceding Annen according to the invention can be used in the claims, characterized in that the hardener 30 to produce heat-curing substances, if these an aromatic polymethylol in combination with polyphenylenes with curable polyphenylenepolyeinem Catalyst is used. kidneys are mixed, as the invention

(See the method according to any one of claims 1 to 4. Such mixtures can be used in any desired way characterized in that a th ratio are used as hardener, depending on the relative Mixture of a polymerizable xylylene hardness and the desired casting conditions. It is glycol and a sulfonic acid is used. accordingly an advantage of the invention that essentially

7. The method according to any one of claims 1 to 4, insoluble and infusible polyphenylenes now in characterized in that an aro process with heat curing is used as the hardener matic polyfunctional sulfonyl halide can be used to make improved thermoplastic products will. 40 see fabrics manufacturing.

8. The method according to any one of the preceding soluble and meltable, branched, completely Claims, characterized in that the partially aromatic polyphenylenes required for the invention wise cured polymer mixture are usable insoluble, have a medium carbon uid infusible polyphenylene polymers that have a hydrogen ratio of about 1.5 or from 1.4 to 1.7. have a higher molecular weight than the sol- 45 Mostly the ratio is between 1.43 and 1.60. borrowed polymers. These polyphenylenes owe their meltability

9. The method according to claim 8, characterized in that, as insoluble polymers, molten presence of phenyl or biphenyl branches or unmelted aromatic ring polymers such as a meandering shape of their longest ket are used as insoluble polymers. ₅ o th. Because of the presence of these branches and the

10. The method according to claim 9, characterized in that the polymer molecule can have a meandering shape indicates that as insoluble polymers predominantly do not assume a flat shape like the pure Parapoly Parapolyphenylenes can be used. phenylene. As a result, the branched polymer molecules not very close together

55 and the extremely high van der Waalsehen

Forces present in pure parapolymers

not observed. The readily treatable (soluble) and meltable polyphenylene polymers are preferred through the polymerization of biphenyl,

The invention relates to a process for the production of terphenyl, quaterphenyl and their branched iso-production hardened molded body made of synthetic resin, at meren. Mixtures of these substances with each other and sodem soluble, fusible polyphenylene polymers in such as with phenylene oligomers and polyphenylene dissolved in a hot solvent and then less than five aromatic rings in here Solution is heated with a hardener for it, so produced in a sophisticated manner.

that a pre-hardened polymer mixture is produced, 65 The extraordinary properties of such dissolves this polymer blend without substantial white and meltable branched polyphenylene teres Curing dried and finally the partial resins can be hardened by the following properties Mixture processed and written into one:

1, you have an excellent Wännebeständigkeit and suffer in the cured state at temperatures between 400 and 500 ⁰ C in a neutral atmosphere negligibly small weight losses.

2: They have average molecular weights from 500 to over 5000, preferably in the range of 1000 ± 500.

3. They are sufficiently soluble in common organic solvents, especially in halogenated hydrocarbons, such as halobenzene, dihalobenzene, trihalobenzene, trichloroethane, tetrachloroethane, Chloroform or toluene, especially in the heat. You can therefore use the Can be used within the process for the production of upper slats and coatings.

4. They are meltable and flow sufficiently at temperatures commonly found in hot casting presses can be used so that they can be processed with conventional machines.

This combination of properties combined with their ease of manufacture and good quality Yield represent a significant advance in the art of wholly aromatic polyphenylene resins Components that can be made with the new resins include electrical insulators, Rocket nozzles and such components that withstand high temperatures for long periods of time have to. Many commercial uses do not require resilience such harsh conditions, and although some of the modified polyphenylene blends disclosed herein can also be used under the above conditions, many are as disclosed herein modified polyphenyls suitable for normal areas of application in which they represent an improvement and extend the scope to areas where such substances were previously unsuitable.

The hardener can be formed from an aromatic polymethylol or one of its derivatives and comprise an acid catalyst. It causes the copolymerization or hardening of the polyphenylenes to an infusible and untreatable state. For example, the hardener can be a xylene glycol toluenesulfonic acid telomer or simply a mixture of the polyphenylene polymers and the hardener can be used in situ, optionally also in combination with treatable and / or untreatable modifying substances. Farther the hardener can use other substances such as polyanthracene, polyindenes, phenylsilanes, polystyrene, polynaphthalenes, Contain polybenzimidazoles or mixtures thereof.

The soluble and meltable polyphenylenes can serve as reactive plasticizers and thereby the Use of relatively large amounts of untreatable multi-ring aromatic resins in the casting preparation enable and good measuring behavior, good homogeneity and other desirable casting properties guarantee. The casting preparation can be made by the application of heat or heat and pressure in the presence of the hardener according to the process according to the invention in the hardened State to be transferred. The amount of the substantially insoluble polyphenylene material and others Additives can be made in terms of the properties desired after curing and the desired Hardness can be varied.

Although a hardener consisting of a polymethylol and the acid of an aromatic compound

not a satisfactory curing of an untreatable one multi-ring aromatic resin can effect, the composite resins which can cause the untreatable multi-ring aromatic polymers and the soluble, meltable, branched polyphenylene contained can be cured homogeneously with the help of such a hardener.

The soluble, meltable and branched polyphenyls used according to the invention are preferably those that have an average molecular

is weight in the range of 500 to 3000, but may also include higher polymers. The soluble and meltable polyphenylenes can with the help a strong Lewis acid catalyst and an oxidizing agent obtained from the following substances that can be used individually or in combination: biphenyl, terphenyl, quaterphenyl monomers or polymers, their isomers or mixtures, including the monomers or polymers of naphthalene, anthracene, phthalene, so-

»5 such as modifications or mixtures of these substances which have soluble and fusible joints with a C: H ratio of about 1.46 to 1.7, and on average 1.5, and in a temperature range of about 90 to 200 ⁰ C. If desired, small amounts of benzene can be used together with the above-mentioned substances. Furthermore, to control the reaction conditions and the end product in the production of the polyphenylene polymer material, variations can go back.

made visible the use of catalyst in excess or the monomer in excess will. The solvent can contain a nitroalkane, such as nitromethane, which is associated with the Can participate in the polymerization process. A general picture of the manufacture of the invention The following example gives the polyphenylene used.

A mixture of 35.6 g of technical anthracene, which contains 30 to 40% anthracene, 20% phenanthrene and 20% carbazole, and 53.3 g of anhydrous aluminum chloride is heated to 120 ± 4 ° C. Over a period of 20 minutes, 53.3 g of anhydrous cupric chloride are added in small amounts and introduced into the mixture. Heating and stirring are continued for an additional 25 minutes. The reaction mixture is then cooled, carefully washed with concentrated hydrochloric acid and then with water. After the subsequent drying, the crude product obtained in this way is placed in a Soxhlet extractor and extracted for 24 hours with a solvent mixture consisting of 15 percent by volume benzene and 85 percent by volume naphtha. The insoluble residue is then extracted with chlorobenzene for 24 hours. The product soluble in chlorobenzene was the useful polymer. It weighed 12.5 g and melted at 165 to 280 ^0C .

In another example, a mixture of 46 g (0.2 mol) of orthoterphenyl and 30.8 g (02 mol) of bipheny! and 108 g (0.8 mol) of anhydrous copper (II) -

Chloride heated to 135 ^{0 C.} With continued stirring, 145 g (1.1 mol) of anhydrous aluminum chloride were added in small amounts over the course of one hour. The mixture was then

5 ^{ 6

be for 3 ¹ J ₄ hours at a temperature between mere, which are essentially insoluble and infusible

158 and 180 ⁰ C held. The inorganic salts can be separated from the main product,

then by repeated washing with 6N salt example 1
acid and subsequent multiple washes with

Water removed Removing these salts can also 5 300 g of polyphenylene polymer with a

with 6N to 12N hydrochloric acid or with 12N hydrochloric acid melting range from 160 to 180 ° C and an average

alone and subsequent washing with water he molecular weight of about 700 to 1000 in 600 ml

follow. After the washed product continuously trichlorethylene, which is heated to boiling point

was dissolved in a Soxhlet extractor with a boiling mi. A hardener solution was used

quenching of benzene (15 to 20%) and cyclohexane 2 io from 150 g of p-xylylene glycol, 45 g of p-toluenesulfone

After extracting for days, the product became acid hydrate and 500 ml of chloroform by 20 hours

had been continuously refluxed for one day with hot chlorobenzene,

extracted that was boiling or near boiling. The azeotropic distillation produced during water

Chlorobenzene solution was removed to a small amount.

concentrated and the polymer with cyclohexane. 15 The polyphenylene solution and the hardener solution were

pleases. 10.8 g of polymer were obtained, which were then mixed and taken for 20 hours

180 to 220 ⁰ C melted. Heated to reflux. After cooling became a part

In another example, a mixture of the varnish with parapolyphenyls was mixed in a blender with 200 grams of Orthoterphenyl (0.87 moles) and 234 grams of anhydrous high shear to form an on-cupric chloride (1.74MoS) with continued slurry showed that about two parts by weight to 150 ^c C PolyRühren heated. Then, while phenylene xylylene glycol solids were added to 1 part by weight of a time of about 2 hours during which the tempe contained parapolyphenyls. The mixed paint was kept temperature at 150 ± 10 ⁰ C, 116 g of water then for coating dry carbon fiber-free aluminum chloride (0.87 mol) was periodically added, which was then dried in the air and given. During the next 3 hours then 25 for 10 minutes at 7O ⁰ C in vacuo geweitere 117 g of copper (II) chloride (0.87 mol) in portions was dried. This intermediate was then added wisely. During this time the polymer solids became 48 percent by weight.
The temperature was kept at 160 ± 10 ^° C. After termination of 21 layers of this intermediate were then supply the reaction, the crude product was carefully overlaid and at 200 ⁰ C and 35 kg / cm ² wähzuerst with concentrated hydrochloric acid, then pressed with dilute 30 rend 2 hours. The laminates then weighed in the acid and finally washed with water. After the 339 ± 1 g and had a solids content of 46%. The crude polymer was dried in a Soxhlet. They were then post-cured by continuously heating the extractor for 18 hours to 135 ° C. for 4 days with boiling and then extracting water-benzene. In this manner, products are removed in 108 hours on a programmed low molecular weight thermal enzyme. After termination 35 klus subject, wherein the temperature slowly supply the benzene extraction, the crude polymers of 135 to 290 ⁰ C was increased, and were then kept for continuously with boiling 1,2,4-trichlorobenzene 6 hours at 29o C ^0. The layer extracted. The polymer fraction which were materials in trichlorobenzene was ablöslich in the post curing oven at 95 ⁰ C, weighed 67 g, which was cooled to a yield of 33% before they were removed. The cured corresponds to, and melted at 220 to 24O ⁰ C. 40 th laminates weighed 332 ± 1 g each and contained-

A slight modification of the last 45 weight percent polymer described last. Their density was

Example, which consisted in the fact that the additional 1.30 ± 0.02. The cured laminates were

The amount of copper (II) chloride was only 23.4 g (0.17 mol) and the poly contained therein was

gave a soluble polymer of 62.6 g of polymer binder into an insoluble and infusible one

phenylene (yield 31.5%), which converts ^{material at 235 to 25O 0} C 45,

melted. _R. . . «

In general, the polyphenylene has an e 1 s ρ ι e

exhibits poor heat resistance if the higher polymers do not produce a branched poly, low molecular weight fraction (smaller than phenylene xylylene glycol-parapolyphenylene varnish) from the higher polymers by benzene 50, as in Example 1. The paint was then separated for 18 hours at ambient or other suitable solvent and then in a vacuum of 105 minutes. The cleaning step is therefore important. Where it was dried ^{at 70 °} C. for a long time. The polymer mixture allows the intended use, but can then be ground to a fine powder. 32 g of the genie the fusible and treatable polymers dried polymer was made in a press at 26O ⁰ C with advantage use, optionally a poly- 55 and for 2 hours under a pressure mergewicht in the range of 500 to 800 and of 210 kg / cm ² pressed. The pressed body weighed to have a melting point in the range of 120 ± 20 ^° C. 31.8 g. It was then post-cured or baked according to the method described in Example 2 in connection with a suitable hardener can, these polymers for the production of plastic paints. The final weight was 30.3 g. The end product was and colors within the scope of the inventive compression, glossy and completely insoluble can be used. and hardened infusible material.

The untreatable, multi-ringed aromatic. -to

Polymers which are used according to the invention, B e 1 s ρ 1 e I 3

and which are characterized by the fact that they as in Example 1 was a Polyphenylenxylylengly-

essential infusible and essentially insoluble 65 kol lacquer, but instead of the para

are in those solvents in which the soluble, polyphenyls are another untreatable polyphe-

fusible branched polyphenylenes are soluble, nylenes are used. The paint was then at 18 hours

can be parapolyphenylenes or by-product poly- ambient temperature and then vacuum

17th

dried ^{at 70 °} C. for 105 minutes. The polymer blend was then ground into a fine powder. 32 g of the dried polymer were placed in a press and ^{pressed at 260 °} C. and under a pressure of 210 kg / cm ² for 2 hours. The pressed body weighed 31.8 g. It was then cured in the same manner as described in Example 2. The final weight was 30.2 g. The final product was dense, shiny, and completely cured to an insoluble and infusible material.

Such soluble and meltable polyphenylene polymers can be mixed with modifying or modified material in a solvent or in the dry state, and the hardener can then be added in the dissolved or dry state. However, it can It may also be desirable to mix the soluble and meltable polyphenylenes with the hardener and then the modifying or modified material to be added while the soluble and meltable polyphenylenes have not yet reacted or are in are in a partially reacted state, namely in the dry or wet state.

Although, as described above, the polyphenylene is preferably used in polymer form and the The hardener comprising an aromatic polymethylol in combination with a polymerization catalyst in prepolymer form can also be the monomeric combination aromatic polymethylol and line acid catalyst can be mixed with either the soluble polyphenylene polymers or the aromatic monomers that form these polymers and reacted in situ, with constant removal of water, to obtain an inferior but useful soluble product which, as described, advantageously modifies or can be used to produce a thermoplastic, curable composition through the Mixing with it in liquid, plastic or powdery form to modify. Except for the otherwise relatively insoluble and infusible aromatic resin-forming substances, such as, for example, the para and Other polyphenylenes can form such substances as soluble or untreatable and insoluble Polymers of polyphenylene sulfide, polyphenylene oxide, polyphenylenes of the Wurtz-Fittig type, polyphenylenes, which originate from a radiation polymerization of aromatic compounds, highly aromatic natural tars or coal tarp as well as other polymers or resin-forming substances are added to the soluble combination of the polyphenylene polymer and hardener, which replace the specified solid additives in whole or in part or in equivalent proportional amounts. MH or without the presence of such added or a priori insoluble solids present and other modifying or modified material as described was measured when mixed with the meltable and treatable polyphenylene polymers ensure that the solution or reaction phase between the soluble jrad meltable polyphenytes and the hardener for a subsequent hardening and solidification of the Mixture is preserved. Such compound Mixtures can be used indirectly in dissolved, powdery or plastic form in the context of the process according to the invention.

As indicated, those made from curable, soluble and meltable polyphenylene polymers and

Hardening existing mixtures to be hardened in the described manner by adding various thermosetting or thermoplastic Polymers are modified, for example by synthetic rubbers, isobutylene or polystyrene, regardless of whether parapolyphenyls and the like are solids in solution, dispersion or powder form are present, whereby either the heat resistance of the thermoplastic increases and its hardness improves

ίο or vice versa, the hardness of the cured polyphenylene mixture is reduced, depending on the conditions in the solution or powder mixture.

The hardness is preferably a prepared prepolymer solution, which is created by the implementation of an aromatic see, non-phenolic polymethylol compound with an acid catalyst, preferably of aromatic character, one or more sulfonic acids, such as p-Toluenesulfonic acid, benzenesulfonic acid, cyclohexanesulfonic acid and mixtures thereof.

»Ο Acids such as phosphoric acids, alkylphosphonic acids, arylphosphonic acids, alkylphosphonous Acids, arylphosphonous acids, sulfuric acid, strong alkyl or aryl carboxylic acids, in particular halogen derivatives of these acids and mixtures thereof

»5 acids can be used according to the desired ratio of initial polymerisation and subsequent curing, as described. For example a sufficiently strong acid can be used to initiate an initial condensation polymerization and the subsequent curing without effecting the addition of additional acid catalyst, or it a weaker condensation catalyst can be used first and then a stronger catalyst Curing can be added or it is as needed

3S a combination of such catalysts is also possible.

The condensable aromatic hardener is essentially, as indicated, an aromatic poly methylol compound with the structural formula

CH ₈ OH

5 «or

HIGH ₁

HIGH,

CH ₂ OH

""., CH ₁ OH

Here X is either —O—, —S—, - SO, - -CH ₁ -,

or

including mixtures of these substances. The other Ring substituents can be hydrogen, alkyl, aryl, alkaryl, aralkyl, alkoxy or aryloxy radicals and so on their tallowly halogenated derivatives, the sterisc do not hinder.

50964Qfl

r si

10

The above examples illustrate a preferred reflux and yielded 649 g of a varnish with

tes method of using mixtures with a solids content of 18.5%.

which is a typical and preferred type of polyphenylene. .

Prepolymer solution is used. Other solutions example 6

can using aromatic poly- 5 From 50 g of recrystallized p-xylylene glycol, 16 g

methylol monomers and an acid catalyst or toluenesulfonic acid hydrate and chloroform was through

their polymers and mixtures of these substances, heating the stirred mixture in reflux while

and the solids and / or other modi rend 20 hours and continuous dehydration

fied or modifying synthetic resin-forming material - a hardener solution has been produced. Then it became

material contained in the manner disclosed herein where chloroform is removed under vacuum while the temperature

that is. As indicated, the curing agent is temperature was preferably kept below 50 ⁰ C. The solid part

used as prepolymer, for example as polymer, was then redissolved in dioxane,

oxyxylylene, derived from the above compounds. The above solution was then mixed with a solution of

has been derived by reaction with an acid. 60 g of polyphenylene with a molecular weight of

The following examples are intended to further apply about 1000, a carbon-to-hydrogen ratio

show dung. of 1.57 and a melting range of 140 to 182 ° C

Example 4 ^{and 40} 8 aromatic coal tar pitch in 200 ml

mixed p-dioxane. The combined mixture was

There were then heated 40 g of polyphenylene with a molecular 3 ¹ / »hours at 70 ⁰ C to give

weight of 1000 and a melting range of 160 ao 826 g of a lacquer with a solids content of 18%.

up to 200 ⁰ C and aromatic coal tar pitch in 150ml The use of components and solvents,

dissolved p-dioxane. For the hot solution, as listed here, the temperatures were added

a hardener solution is added, which consists of 20 g 1,4-xylylene and the reaction and hardening times depend on the special

glycol, 6 g p-toluenesulfonic acid monohydrate and 150 ml len mixture and the desired end results

Consisted of chloroform. The hardener solution was before »5 as it can now be easily seen. Continue is now

was added to the poly-ethylene solution, under noticing that the aromatic monomers that make up the

Constant dehydration for 20 hours under reverse aromatic melted and unmelted

fi has been heated. The combined polyphenylene- polyphenylene polymers form with the hardener in

Xylylene glycol solution was then mixed for 6 hours on monomeric or polymeric form

70 ° C heated. When completed, it weighed 381g.

and contained 21% solids. This lacquer was, as a given procedure, an in situ reaction of a

Impregnating varnish suitable and proved to cause partial hardening for reinforcement, in the case of the preferred

of fibers as useful. wisely maintain solubility and meltability

will. The proportions in which the compo-

B e i s ρ i e 1 5 35 nents are mixed, depend on the desired end result in terms of final hardness, suppleness

A hardener solution was used, which was determined by the strength, toughness or flexibility of the more or less

30 g p-xylylene glycol, 9 g p-toluenesulfonic acid hydrate ger plasticized aromatic polyphenylene or

and chloroform with heating for 20 hours in the desired increase in heat resistance

Reflux with continued stirring and water off the thermoplastic material. In the case of the invention

withdrawal has been established. This solution was then made according to the process can be neutral inorganic

to a solution of 60 g of polyphenylene with a Mo or organic fillers and mixtures such

average weight of 1000 and a melting range fillers of the usual type can also be used, as in both

from 160 to 200 ⁰ C, 30 g of an aromatic carbon, for example natural or synthetic rubber,

tar pitch and 180 ml of trichlorethylene were added. 45 cellulose, synthetic fibers, metal oxides, silicate «

The combined solutions were then 20 hours or silica and the like.

Claims (4)

fully hardened product is baked. Claims: The polyphenylene polymers used according to the invention comprise separately produced polymers 1. Process for the production of hardened molded and / or in situ formed polymers and / or mixed bodies made of synthetic resin, thus identified by monomers and polymers. ζ e i c h η e t that soluble, meltable polyphe- The method according to the invention leads among other things Nylenpolymere in a hot solvent rem to cast or pressed, cured dissolved and then the solution with a hardening components for the production of coatings or ter is heated for it, so that a pre-cured of laminates of high strength and high Polymer mixture arises that then this poly- io heat resistance. intermixing without significant further hardening In many applications in casting technology dried and finally the partially hardened ßens and pressing and the production of components It is essential to have a mixture processed and made into a completely high heat resistance cured product is baked. To use polymer of high heat resistance, 2. The method according to claim 1, characterized in that 15 records a high molecular weight from the outset, that soluble polyhedral polymers with or during the casting or fabrication process Molecular weight between about 500 and cross-linked to a high molecular weight, from-3000 be used. can be hardened or vulcanized. At the same time is 3. The method according to claim 1 or 2, characterized in that the polymer is meltable, that is characterized that as soluble polymers Anthra- 20 under the heat and pressure conditions as they cen-, naphthalene-, phenanthrenes, biphenyl-, ter- in the casting and manufacturing process application finphenyl- or quaterphenyl polymers or mids, is flowable, and that the uncured polymer These polymers can be used. is soluble in common solvents, so that filling 4. The method according to one of the preceding fabrics, fibers and the like. Before casting or a Claims, characterized in that the other »5 manufacturing process with the polymer solution A halogen hydrocarbon solvent that can be mixed intimately.