DE1769471A1 - Phenolic Resin Foams and Processes for Making Them - Google Patents

Description

8000 Munich 25,

postfich no. Di pi.-Ip g. R. Pf. Bahr β, ™ *, ™ stnt · η.

Pat-Anw. Herrmann-Tranlepohl "IM I CII. E_t in ■ Pat-Anw. ietiler

Telephone: 51013 USpi.-FIiy *. Ε € ΙΙΙ3Γ «Ι Β & ΙΖίβΓ Telephone: 398011

398012 398013

_gman s: r

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λ * j f% η ι π * Bavarian Association Bank Munich 952287

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Munich

Compagnie de Saint-Gobain, Neuilly-sur-Seine, France

Fire resistant phenolic resin foams and processes too

their manufacture

The invention relates to fire-resistant phenolic resin foams and methods of making them. ·

It is known that the foams made from phenolic resins with g

a high insulating capacity, which have been freed from water and the acid catalyst by tempering, have the disadvantage, that they, if they are exposed to prolonged exposure to a flame be exposed, even after the end of the action of the same continue to damage yourself without a flame, what to completely carbonize the cellular structure of the

Substance leads.

It is also known, in the phenolic resins used for the production of high density foams nitrogen-containing compounds such . B. in particular ureas

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and the ammonia salts. Two phases are observed in this manufacture:

1. A release of heat from the phenol-formaldehyde condensation stems from

2. Above a certain temperature, those containing nitrogen react Compounds violently with the excess of the formaldehyde not combined with the phenol in the presence of the acid catalyst, which causes a very rapid hardening

^ tion of the resinous complex mass causes.

It is now impossible to control the response to what to cellular products with a heterogeneous structure, "it leads to voluminous (large) cells that often have cavities * In addition, the distribution of matter is irregular, the apparent density (raw density) shows great Differences on what these products have very poor insulation, mechanical and fire resistance properties confers.

The aim of the present invention is to provide a process which allows phenolic resin foams to be produced represent that have a particularly remarkable fire resistance, a homogeneous structure, cells with regular dimensions and have good mechanical properties.

The inventive method consists in the phenolic resin before foaming to introduce a nitrogenous organic or mineral compound that has little or no does not react at all with the free formaldehyde of the resin and at the production temperature compared to the foaming The compositions used is stable, this nitrogen-containing product under the action

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The heat releases a gas mixture that does not sustain the combustion.

This nitrogen-containing compound leads to the formation of a complex polymer.

These nitrogenous. Compounds can be selected from aminoplast resins condensed by rope. In particular, products can be used which are formed in the reaction of formaldehyde with urea, melamine, cyanogen λ diamide or any general amine.

It is advantageously used as nitrogen-containing Derivatives that are incorporated into the phenolic resin before foaming

1. Condensates of phenol, formaldehyde and a nitrogenous one organic material, such as B. urea, melamine or dicyandiamide,

2. Condensates of formaldehyde and a nitrogen-containing organic substance, such as. B. urea, docyandiamide

or melamine, the like

3. Misenkendensate of formaldehyde and nitrogenous organic substances, such as those mentioned above,

4. nitrogenous mineral products, in particular Ammonia salts, such as. B. ammonium sulfite or ammonium sulfamate.

These nitrogen-containing compounds, due to their weak reactivity, allow the hardening reaction to take place instantaneously to regulate the foaming and also the density

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of foam (especially with regard to the production of high density products iii of the order of magnitude from 30 to 200 kg / nr) Tand the regularity to regulate the dimension of the pores and thereby the mechanical properties of the end product, in particular to improve its compressive strength *

The phenolic foams which can be produced by the process according to the invention have excellent properties Heat and fire resistance

Under the influence of heat, the nitrogen-containing compounds decompose to release a mixture of grasses, mainly ammonia, and nitrogen Eohlendioxyd _r which an inert atmosphere is created, the combustion can not even in the talk.

The nitrogen-containing compounds are also selected so that they release a maximum of gas when the Burning the cured phenolic resin could sustain itself.

As the resins, there can be used, for example, the following resins, which are obtained by using basic Catalysis a phenol condensed with formaldehyde in aqueous solution or in the form of the polymer.

Resin 1

Phenol 1 mole

Formaldehyde 2.3 moles

NaOH liquor 3 »6 wt .- ^ of the phenol

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Resin 2. ,

Phenol 1 mole formaldehyde 2.5 moles Barium oxide

Ba (OH) ₂ * 8H ₂ O 8.3 wt. # Of the phenol of BaO

Resin 3

Phenol 1 mole formaldehyde 2.3 moles

Polyvinyl alcohol 8.75 wt. # Of the phenol I.

NaOH liquor 3.6 wt. # Of the phenol

Harz 4

Phenol 1 mole of trioxymethylene 2.3 moles of NaOH liquor 3 »6% by weight of the phenol

According to the process of the invention, a phenolic resin, in particular z. B. the resin 1, in aqueous Solution for:

1. a foaming agent which can be a liquid with a low λ boiling point selected from aliphatic hydrocarbons or halogenated derivatives of these hydrocarbons;

2. a mineral filler, for example talc, silica, kieselguhr, asbestos, mica, etc.

3. a nitrogenous compound of the above specified type,

4. a hardener that is a mineral acid or an organic one Acid is.

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This causes the exothermic polymerisation of the resin, wherein the heat generated in the reaction is sufficient to to evaporate the foaming agent, which expands the mass.

According to the present invention, mkn can also mix a silicone oil with the resin and the foaming agent, which has surface-active properties and in particular silicone oils of the mixed polymer-silicone-glycol type, which are water-soluble and stable in solution, according to the information in French patent 1,462,228 of the applicant . The nitrogen-containing product as defined above is then added to this mixture.

One embodiment of the method according to the invention is carried out in the known methods with the aid of a turbine or a device that allows the ingredients to be mixed and dosed at the same time, then with one continuous casting carried out.

The weight ratios based on 100 parts by weight of dry phenolic resin are as follows:

1. Silicone oil about 0.5 to 5 and preferably

about 1.5

2. Foaming agents 1 to 30 according to density

3. mineral filler about 5 to 30 and preferably

wise 5 to 10

4. nitrogen-containing compound (dry matter) about 1 to 30

5. Acid, about 5 to 20 and preferably 3-e.g. HCl, d β 1.19, about 15.

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Below are some examples of the invention Embodiments specified:

example 1

Resin 1 100 £ silicone 1 , 5 g ground ammonium
Sulfamate 15th δ Freon 11 5 G Hydrogen chloride
acid, ds 1.19 ■ 15th G Example 2

Resin 1 100 g

Silicone 2g

Condensate A * 25g

Freon 6g

Hydrochloric acid, d = 1.19 15 g

Condensate A * t resulted from the condensation of 1 pint of dicyandiamide with 2.1 mol of formaldehyde.

Example 3

Harz 4 100 g silicone 2 g Condensate A * 20 g Talk 5 g Freon 11 10 g Hydrogen chloride acid, d * 1.19 15 g

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ί / 69471

Example 4 100 g Resin 1 1.5 g silicone 66 g Condensate 1 * 5 g Kieselguhr 8.5 g Preon 11 Hydrogen chloride 15 g acid, d β 1.19

Condensate A * ; formed in the condensation of 1 mole of dicyandiamide with 2.1 moles of formaldehyde;

Condensate B * t formed in the condensation of 1 mole of phenol, 2.3 moles of formaldehyde and dicyandiamide (25% by weight of the phenol).

The following advantages in particular can be achieved by the method according to the invention

- An improvement in the density of the foams obtained, which can be staggered between 30 and 200 kg / m,

- perfect regularity of the dimensions of the pores,

- good mechanical properties of the product and in particular good compressive strength,

- a remarkable fire resistance j according to the ASTM test D 1692-59 T, the foams obtained are classified under the self Ib * seeing s.

The tempering of the expanded foams is necessary in order to free the foam from residual water and making it non-corrosive by removing the acid. This mode of operation is generally limited by the tempering temperature (about 100 ° C), because the risks

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the char are great. The visual foams according to the invention "have higher heat resistances, can with higher temperatures (about 120 ° C), which significantly reduces the dwell time in the drying cabinet.

It should be noted that the present invention is in no way restricted by the examples given above, but also includes all variants.

Patent claims:

10982B / 1590

Claims (2)

- ίο - claims: 1. Process for the production of fire-resistant phenolic resin foam, characterized in that a nitrogen-containing resin is added to the phenolic resin before foaming or introduces organic or mineral compound that has little or no contact with the free formaldehyde of the resin reacts and at the manufacturing temperature with respect to the compositions used for foaming is stable, this nitrogen-containing product under the action of heat, releases a gas mixture that does not sustain combustion. 2. Modifications of the method according to claim 1, characterized characterized in that they in particular the following, individually or in various combinations have taken characteristics: a) the nitrogen-containing compounds are selected from the partially condensed amino resins, b) the nitrogen-containing compounds arise in the Reaction of formaldehyde with urea, melamine, docyandiamide or any amine in general, c) The nitrogenous compounds used are condensates of phenol, formaldehyde and a nitrogenous one organic material, such as B. urea, dicyandiamide or melamine, d) the nitrogen-containing compounds used are condensates of formaldehyde and a nitrogen-containing organic Substance, such as urea, dicyandiamide or melamine, e) the nitrogen-containing compounds used are mixed condensates of formaldehyde and nitrogen-containing organic substances according to c) and d), - 11 109828/1590 i-iW JvVc - f) the nitrogenous compounds used are nitrogenous mineral products, in particular Ammonia salts, e.g. B. ammonium sulfite or ammonium sulfate, g) one works in aqueous solution, h) m the resin, the foaming agent, the nitrogen-containing compound and the fillers, if necessary, a silicone oil which has surface-active properties, and in particular silicone balls of the copolymer-silicone-glycol type, which are water-soluble and stable in solution, ' i) the foaming of the resin is carried out in the presence of the constituents as indicated below Quantities based on 100 parts by weight of dry resin carried out Silicone oil about 0.5 to 5 »in particular about 1.5, Foaming agent 1 to 30 according to the density, more mineral about 5 to 30 and preferably Filler 5 to 10, nitrogenous Compound 3 about 1 to 30, g (dry fabric) ■ ^x . " Acid (e.g. HCl, about 5 to 20 and preferably . α β 1.19) © around 15. 3 «As new industrial products, phenolic resin foams, characterized in that it according to the ASTM test method D 1692-59T among the © 3 self-releasing Products are classified. 109828/1590