DE1920329A1 - Resin mixture containing filler - Google Patents

Description

Haveg Industries, Inc. (US 724 2? 1 and 724 23Q Wilmlngton _T Del .. V.St.A. prio April 25, 1968

220-225-OBR - 6 * 94) Hamburg, April 21, 1969

Resin mixture containing PUlletoff

The present invention is based on filler Holding resin mixtures, in particular cast or mold resins based on a phenol-aldehyde and / or furfuryl alcohol « Resin.

It is known to thermosetting phenol-aldehyde »resins and To use furfuryl alcohol resins as casting or molding resins However, the deformed products have the disadvantage that they are after repeated heating with intervening cooling or cracks after a few months of use

The purpose of the present invention is to filler with this containing resins to reduce the formation of cracks, to increase the breaking strength, the shrinkage capacity in the mold when processing the filler-containing resins and the disadvantages caused by the Porosity yield »eliminate.

To solve this problem, a filler-containing Harxml8ohung, in particular a casting or molding resin Based on a phenol-aldehyde and / or furfuryl alcohol resin proposed, which is characterized in that it is polymeric monoolefin, preferably in amounts of not more than 10 and in particular from 1 to 5 oew. $ on the oesam mixture contains · In particular are as

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polymeric monoolefins those compounds are suitable which have a softening point of over -4 "25 ⁰ C and preferably over 135 ° C; in particular, polypropylene" but also poly-5-methylbutene or poly-4-methylpentene are suitable.

The polymer, particularly polypropylene, is used in quantities of not more than 10 qew, $, preferably in amounts of 1 to 5 and special in quantities of 3 to 4 Oew.jS der Total composition used.

As fillers, which are preferably used in amounts of 30 to 70 Weight $ 6 are used, come inorganic fillers, in particular graphite, coke, silica and / or asbestos in question, whereby anthophyllite is preferably used as asbestos.

A particularly suitable resin is composed of 30 to 70 OEW.% Filler or preferably 50.5 wt. £ graphite, of from 30 to 69 weight. F> and preferably 46.5 wt. # Phenol-formaldehyde "resin and 1 to IC wt. %, preferably 3 wt.% polypropylene.

The phenol = aldehyde resin is expediently a heat-resistant one Resin and in particular a phenolic or cresol resin.

When using a furfuryl alcohol resin, in particular in quantities of 30 to 68.5 Gew.j6 0.25 to 10 Gew.jU » and preferably up to 3% by weight of a catalyst used for crosslinking and / or condensation of the resin. as Resin can also be a Fortnaldehyd-Furfurylalkohol-Mlschpoly = » merisat, especially with a salary of up to £ 30 Formaldehyde.

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A sulfonic acid salt is particularly used as the catalyst an ammonium salt in sulfonic acid and preferably a Ammonium salt of a benzene and / or toluenesulfonic acid used · As a latent catalyst, the catalyst can be dry or dissolved in water.

Wood flour, walnut shell flour, Coconut flour, sawdust or Botholzmehl, but preferably inorganic fillers such as silicon dioxide, carbon black or coal dust, finely divided graphite or asbestos, o Anthophyll is particularly suitable as asbestos * Asbestos and Chrysotile Asbestos «.

The heat-treatable phenol-aldehyde resin is made from phenol, Cresol, such as a mixture of ra- and p-cresol, made from p-cresol or cresylic acid, xylene with aldehydes such as formaldehyde and furfural »Preferred hard resins are alkaline condensed phenol-formaldehyde resins "

The amount of the phenolic resin is preferably in the range from 69 to 30 Cew.56 of the Gea bath composition and expediently corresponds to seven times the amount of the polypropylene; that is, the polypropylene should not make up more than 1h weight of the resin; preferably about 15 times the amount of resin is used as the polypropylene. Before casting, the Kar2.mlsch.ung is processed in a conventional manner, for example according to US Pat. No. 2,8-5,107, on a mandrel.

It was found that by adding small amounts and amounts up to 4g # of polypropylene to a phenol « Formaldehyde without filler the properties of the poly-

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propylene mixed resin are not as good as at Phenol-formaldehyde resins, which are only an inorganic Fillers such as graphite or asbestos contain «As a result . it is surprising that the addition of low Kengen Polypropylene to a phenol-formaldehyde resin with filler leads to an extremely clear improvement «The addition from small amounts of polypropylene to phenol-formaldehyde resins with fillers such as oraphite, asbestos, finely divided coke or silica, eliminates the existing ones Difficulties in terms of porosity and shrinkage P (slumping) or collapse during further processing.

It was also found that the addition of small amounts of polypropylene to a filled one Phenol ~ formaldehyde = resin cracks at temperature

Fluctuations during heating and cooling and after a long period of time Avoids use. As a result, thicker shaped pieces of wall sections can now be produced without cracking will. In addition, the new casting resins show one better chemical resistance, for example to mixtures of hydrofluoric acid and sulfuric acid, so that this Material is ideal for storage containers.

"Phenol-aldehyde resins can be used as the starting resin in accordance with the US petition 2 835 107, 2 471 6jl and 2 424 787 but other commercially available thermosetting phenolic resins are also available be turned.

In the following, the invention will be based on examples be explained in more detail; In all examples, a finely divided polypropylene was used as the polymeric monoolefin For the rest, all quantities relate to the weight.

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example 1

46.5 parts of phenol = formaldehyde resin according to example 1 of US Pat. No. 2,6 * 35,107 were mixed with 50 * 5 files of powdered graphite and 3 parts of polypropylene with a density of 0.90 and placed on a mandrel or a ⁴ Spindle machined and then deformed into a storage container * After compression molding, the storage container was hardened at a maximum temperature of 135 °. The container was then repeatedly subjected to a heat test in which it was heated to 135 ° C. for 2k hours and then cooled to room temperature. No cracks were found after 10 such treatments. The cast container showed improved resistance to hydrofluoric acid and sulfuric acid compared to phenol-formaldehyde resins with graphite as filler but without propylene.

Example 2

The procedure was analogous to Example 1, but now coke meal was used as filler. Auohler showed There is no porosity and no shrinkage or collapse in comparison with a molding resin without propylene Machining on a mandrel or in the spindle; there were also no cracks after several months of use, which occurred easily with casting resins of conventional composition.

When using furfuryl alcohol »resins either Homopolymers or copolymers with up to 30 wt. £, • ie for example 1 to 30% by weight of formaldehyde or furfural A resin is used which is a copolymer of furfuryl alcohol and formaldehyde and 10 to 20 % By weight contains formaldehyde. The furfuryl alcohol is in ^

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Amounts from 68.5 to 30 Oew.jS, based on the Oe including its composition.

All catalyst can be a liquid catalyst in "aqueous solution, namely an amine or an ammonium a Iz of an Omani sulphonic acid such as an aliphatic or aromatic sulphonic acid, such as dimethylaminobenzene sulphonate, diethylamino = p-toluene sulphone t, ammonium benzene sulphonate, ammonium phenol disulphonate, Ammonium naphthalenesulfonate, ammonium anthracene sulfonate, ajamonium sulfanilate, ammonium p ~ toluo I = * sulfonate Aminonluin-m-toluene sulfonate, Amroonlum-Ό-toluenesulfonate, ammonium anthracene disulfonate, ammonium sulfonates, ammonium sulfonates, and ammonium sulfonates, ammonium sulfonates, and in particular ammonium sulfonates, ammonium sulfonates, and pyrenesulfonates of toluenesulfonate, and aniline salts of benzenesulfonates, and in particular, ammonium sulfonates of toluenesulfonate, and aniline salts of toluenesulfonate, and, in particular, aniline salts of benzenesulfonates of mixtures of benzenesulphonic acid and p-toluenesulphonic acid.When such mixtures are used, they are usually used in a ratio of ItI, although such mixtures are used in a ratio of 1:10 to 10: 1 can rden. These catalysts are suitable as latent catalysts for the conversion of an originally liquid purfuryl alcohol resin into an infusible, non-meltable resin = document 2 499 273 are described. The amount of water present "should be sufficient to dissolve the catalyst". The upper limit is not essential. "However, there is no advantage when using larger amounts of water, since these then have to be removed by evaporation * The active catalyst is preferred, that is," the salts of sulfonic acid, including water, in quantities of $ 1

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of the mixture and generally one used in amounts from 25 to 10 % and preferably in amounts from 0.5 to%. It is essential that the catalyst is present in such amounts that the resin is condensed and crosslinked in the usual manner.

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Dry catalysts such as aroin or ammonium salts of organic sulfonic acids can be used, and organic sulfonyl chlorides such as p-ToluoX ”= sulfonyl chloride or Eenzclsulfonylchlorid or other catalysts, as described in US Pat. No. 2,499,275, can be used . When using asbestos as a filler, the addition of the polymeric monoolefin improves the furfuryl alcohol resins, which contain dry catalysts. In the case of furfuryl alcohol "resins, the catalyst is preferably used in liquid form, i.e. in an aqueous solution"

In the previously known -m Fm * furyl alcohol <= Fos ⁱ jnaldenycU resins with graphite as filler and a dry mixed catalyst of ammonium benzene sulfonate and arcrcorJum p toluenesulfonate and p-toluenesulfonyl chloride, considerable difficulties arise with regard to crack formation. The use of asbestos instead of graphite also resulted in cracks, especially in thick-walled molded parts _o By using liquid catalysis when using graphite as filler and when using a combination of polypropylene and liquid catalyst when using graphite as filler, even greater improvements are achieved and the crack formation completely abolished

When using asbestos as a filler, the Use of liquid ketalyzers posed some difficulties

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with regard to tearing or reaming corrected will. The use of polypropylene in combination with a liquid catalyst when mixed with asbestos Resins led to an even further improvement in various properties "but was not particularly outstanding like the improvement that old graphite as a filler in Kombinatlon with polypropylene and liquid catalyst was achieved instead of just liquid catalyst, with the exception that considerably higher values for elasticity were achieved and pressure deformation at the presence of polypropylene have been achieved «

In addition to the advantages already mentioned the liquid catalyst system has the advantage according to the invention with calibration that it is mixed with the furfuryl alcohol resin is stable for more than a day. However, if you have a solution If Kars is made from furfuryl alcohol with the catalysts known up to now, this is the stability of this system no more than a working day, then one defl fresh approaches of catalyst and furfuryl alcohol resin every day anew manufacture oni.

The liquid Katalyaatorsysteae geaäas invention can with p-toluenesulfallyl chloride or benzenesulfonyl chloride or ■ it the free sulfonic acids, such as with p-Toluenesulfonic acid are added, but not laawr is required.

Di «rurfurylalkohol-Hariaa.acnuncen are deformed before dta in a tibial manner as in US Pat preprocessed on an agile spindle or on a «mandrel.

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The use of polypropylene and a liquid Katalyaatorayatem not only eliminates the difficulty of cracking, but also improves chemical resistance and the phyaika-like properties of the deformed Purfuryl alcohol resins, such as vegetable U.S. Patents 2,835,107, 2,499,274, 2,471,438, and 2,471,631 can be obtained

Example 3

52 parts of furfuryl alcohol-formaldehyde resin were prepared according to Example 2 in accordance with US Pat. No. 2,835,107. This resin containing about 20 % formaldehyde was mixed with a catalyst solution composed of 0.43 part of ammonium benzene sulfonate and 0.39 part of ammonium p ^ toluene sulfonate dissolved in water. 47.18 parts of anthophyll asbestos were added to this mixture. This mixture was then processed in a spindle according to US Pat. No. 2,835,107 and shaped into a storage container in the usual way Cooled down to room temperature. After 10 of these similar events, no Rlsee could be noticed.

Example 4

52.O parts of a furfuryl alcohol-formaldehyde resin according to Example 3 were made with 0.34 parts of ammonium benzene sulfonate and 0.30 parts of ammonium p-toluene-ulfonate in a small amount Dissolved excess water mixed. This mixture were

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0.18 part of dry p-toluenesulfonylochloride and then 47.18 parts of AnthophylUt-Atbeat sugeaetst. The Mlaohung was then further processed analogously to Belaplel 3 and become one Reservation ostracized, represent the same properties showed.

Beiaplel 5 ^

46.32 parts of the purfuryl alcohol-forraaldehyde resin, just in example 3, were removed with a liquid catalyst _; -, 0.48 part of ammonium benzene sulfonate and 0.40 part of ammonium p-toluene sulfonate mixed in Waaaer, mixed with 0.24 part of trookenen p-Toluolaulfonylohlorld and anachiiοBand with 52.56 parts of graphite. The mixture was processed to tile Ublioh and shaped into a torrate container and cured at 135 ° C. The output of this container corresponds to that of the container according to Examples 6 and 7, in particular with regard to the deformation, the elasticity and the tensile strength, but the properties were better than when a completely dry catalyst was used.

Example 6

46.5 parts of the resin according to Example 3 were with a Catalyst dissolved in water from 0.5 parts each Ammonium benzene sulfonate and ammonium p ^ toluolaulfonet yer ^ With 3.5 parts of polypropylene with a density of 0.90 and 49.0 parts of oraphite. The mix was processed into slnss container as in example 3 and at 135 ° gehUrtst · "aoh 10 heat treatments showed up

no cracks, and deformation properties and larger Tensile strength compared with a no containing resin were clearly recognizable.

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Bei Piel 7

46.52 parts of the vegetable Beißpiel 3 resin used were with 0.48 parts AaunoniumbenzolBUlfonat and 0.40 Parts of ammonium «p-toluenesulfonate dissolved in water mixed, whereupon 0.24 parts of dry p-toluenesulfonylchloride and 3.5 parts of polypropylene and 49.06 parts of graphite were added became. As before, a storage container was made, which after curing at 135 ° in its properties Container according to Example 6 corresponded.

Example 8

The procedure was analogous to Example 6, but the process was steep anthophyll asbestos has now been used by graphite. The container produced in this way has a wall thickness of several inches showed no cracks! auoh the Deformungselgensohaften and the tensile strength were better than a container according to Examples 1 and 2.

Example 9

52.0 parts of the resin obtained in Example 3 were 0.34 parts of AeeMtiluetbensolaulfonat and 0.30 parts of Aenaoniua * p-toluenesulfonate, applied in a slight "excess Was" tr, as well as 0.18 parts of dry "p-toluenesulfonyl chloride and 3 , 0 parts of polypropylene and 44.18 parts of Anthophylilt-Asbeat vemleoht "The container made from this resin as mentioned above corresponded to" a properties hardness at 135 ° * * * condensation compared to Example 6.

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Settlement processed: 1.25 parts of an acid washed Anthophyll »asbestos, 0.34 parts ammonium benzene sulfonate, 0.31 part of ammonium ^ p ^ toluene sulphate, 0.17 part of p-toluene sulphonyl chloride. This mismatch was then with 44.8 parts Asbestos filler added and further processed according to Example 3, the container produced again at 135 ° C was cured. Significant cracks formed within a day.

Example 11

The procedure was analogous to Example 10, but now 50 parts of furfuryl alcohol-formaldehyde heart, 2 parts of one dry mixture of 1.21 parts of acid-washed anthophyllite asbestos, 0.32 parts of aramoniutbenzenesulfonate, 0.29 part of Amtnoniuin ° p-toluenesulfonate and 0.18 part / i p-Toluolßulfonylchlorid with 5 parts of polypropylene and 43 parts of asbestos filler were mixed. After curing the molding at 135 ° C, it was found after one day thin hairline cracks and after three days numerous small cracks at this temperature "

When asbestos and a liquid catalyst mixture according to Example 3 are mixed with furfuryl alcohol-formaldehyde resin and the product obtained is formed, so has this has essentially the same formulative properties and elongation properties as a corresponding mixture with the same catalyst, but in an anhydrous form has been made.

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Claims (10)

Claims 4lJ resin mixture containing filler, in particular casting or Portnharz based on a phenol-aldehyde »and / or Furfuryl alcohol haraes, characterized in that it a polymeric monoolefin, preferably in amounts of no longer every 10 and in particular from 1 WS 5 0ew, £ based on the total mixture contains 2. Resin according to claim 1, characterized in that the polymer monoolefin has a softening point of over 125 ° C and preferably over 1> 5 ° C and in particular ~ special polypropylene is. 3. Resin according to claim 1 to 2, characterized in that that it as pull material 50 to 70 wt. £ of an inorganic Filler, in particular graphite, coke, silica and / or asbestos preferably contains anthophyllite 4. Resin according to claim 1 to 3, characterized in that that it is from 20 to 70 square feet of filler and preferably 50.5% weight graphite, 30 to 79 weight weight and preferably 46.5 wt. £ phenol-formaldehyde resin and 1 to 10 wt. £ preferably 3 wt. £ is made of polypropylene Resin according to claim 1 to 4, characterized in that it is 1 to Contains 5% by weight of polypropylene and not more than 14 %, based on the resin. 909851/1637 BATH ORIGINARY; 6. Resin according to claim 1 to 5 »thereby gekennzelclinet, that the phenol "aldehyde" Hars is a thermosetting resin, In particular, is a phenolic or cresol resin. 7a resin according to claim 1 to 5, characterized in that the resin is from 310 to 68.5 £ OEW. Of a furfuryl alcohol "resin and 0.25 to 10 wt. £, preferably up to 3 Ctevi _o # a catalyst for crosslinking and / condensation ODSR of the resin. 8. resin naoh claim 7, characterized in that the catalyst is a sulfonic acid salt in particular
Ammonium salt thereof and preferably a salt of a benzene- 'urc ^ / or toluene sulfone & ure isto 9 · Resin according to claims 1 to 8, characterized in that the resin is a Pormaldehyde-Purfuryl alcohol copolymer with up to 50% fonaaldehyde. 10. Resin according to claim 7 to 9, characterized in that that the catalyst is a latent catalyst dry or dissolved in water. ue: sch. 909351/1637 BATH ORIGINAL