DE2857060A1 - PHENOLIC FOAM AND SURFACTANT USEFUL THEREIN - Google Patents

Description

Closed cell phenolic resin foam material, process for the production of such a material, as well as laminate building boards produced from such a material

The invention relates to a closed-cell phenolic resin foam material which is produced from compounds which react to form a phenolic resin, a blowing agent and a surface-active agent, which is a blocked reaction product of an alkoxylated amine and a copolymerizable mixture of a dialkyl maleate and
N-vinyl-2-pyrrolidone or
Is N-vinyl caprolactam.

Phenolic polymers have been known for decades. Recently, there has been particular interest in such phenolic polymers increased, which can be foamed into cellular materials, which are commonly referred to as foam plastics. Such

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Foams are made by having the reactants in the presence a propellant are mixed. Examples of such materials and processes can be found, inter alia, in US Pat. No. 2,744,875, CA-PS 674 181, CA-PS 684 388, CA-PS 866 876, GB-PS 598 642, AU-PS 128 508 and in Modem Plastics Encyclopedia, Vol. 52, No. 10a, p. 479 (1977).

Most known cellular materials made from phenolic polymers, however, show an unsatisfactory initial level Thermal conductivity. Other known cellular materials made from phenolic polymers show an undesirable tendency over time Increase in thermal conductivity.

The aim of the present invention is therefore to provide an improved one phenolic synthetic resin foam material, which has these disadvantages known foamed plastics does not have a high content of closed cells and still has good properties in terms of breaking strength, compressive strength and flame resistance, and which has a high heat resistance and distinguished by good insulation properties and a particularly small increase in thermal conductivity (k-value) over time is.

Other objects of the present invention are an improved one Process for the production of such cellular materials from phenolic polymers and the use of these materials for Manufacture of improved laminate building boards from such closed-cell phenolic resin foam materials with good properties in terms of thermal insulation, heat resistance, breaking strength, sound insulation and static strength.

The invention is explained in more detail with reference to the following description and the drawing; show it:

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Figure I the formula I mentioned below, Figure II the formula II mentioned below, Figure III the formula III mentioned below, Figure IV the formula IV mentioned below, Figure V the formula V mentioned below, Figure VI the formula VI mentioned below, FIG. VII the formula VII mentioned further below, FIG. VIII a cross section through a laminate building board with a top layer,

Figure IX shows a cross section through a laminate building board

two top layers, j

FIG. X shows a graph in which, for foams according to the invention, the thermal conductivity value (K factor) versus j. the time is plotted. ■ j

The invention thus relates to a cellular material with closed cells, which consists of a phenolic synthetic resin, a propellant and a surfactant, the hydroxyl number of which has been suppressed to a value below 50 and preferably below 10, that it has been reacted with a blocking agent. The blocking of functional groups is a method familiar to chemists, and common means for masking the hydroxyl functionality are, for example, those compounds which lead to the formation of esters , urethanes and ethers.

Phenolic resin foams are also a well-known class of materials; Phenol aldehyde resin Foam is a typical representative of this, and the proportions to be used for propellants and catalysts and resin components are familiar to anyone skilled in the art.

Low friability foams can be obtained, for example, by using a preferred phenolic polymer, the is described in U.S. Patent 3,876,620. A preferred phenolic

1 polymer is that with the formula I (Figure I), in which R for

HOCH-, hydrogen or a radical with the formula II. R ⁴

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2
The R radicals consist, independently of one another, of lower alkyl groups, phenyl groups, benzyl groups, halogen atoms, nitro groups or hydrogen atoms. The R radicals consist, independently of one another, of HOCH groups, hydrogen atoms or a radical

■ k *

with the formula II (Figure II).

4th
The R radicals are, independently of one another, lower alkyl groups, hydrogen atoms, phenyl groups, benzyl groups or furyl radicals. The furyl residue is the group that is introduced when using furfural.

In formula I, χ is an integer from 2 up to and including 10 and preferably from 2 up to and including 6. If χ is less than 2, the result is a foam which is too brittle. On the other hand, when χ exceeds 10, the viscosity of the polymer increases to such an extent that production the foam is difficult.

The phenolic polymers according to the invention generally have a molecular weight between 200 and 2000, preferably between 300 and 1500. At lower molecular weights, the foam formed tends to be very brittle, while at high molecular weights the viscosity of the phenolic polymer, even when a solvent is present, is so high that it can be processed is no longer possible.

A preferred subgroup of phenolic polymers is that of the formula Ili (Figure III). In this formula III, R stands for HOCH ₉ -, hydrogen or a radical with the formula IV

3
R radicals are, independently of one another, HOCH ₂ groups, hydrogen atoms or radicals with the formula IV (FIG. IV).

According to a preferred embodiment of the invention, at least

3
At least one of the R radicals is a methylol group, i.e. HOCH ₂ -. In order to

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it is ensured that there are crosslinking points on the phenolic polymer are located. Such methylol groups or, if the aldehyde is other than formaldehyde, alkylol groups become automatically introduced into the polymer in the process described below in a manner known per se.

In the polymers according to the invention, the ratio of the radicals with the formulas II or IV to give o-cresol units vary within a wide range. In general, this ratio lies however between 1: 3 and 10: 1 and preferably between 1: 1.5 and 5: 1. With higher ratios, i.e. with a lack of o-cresol, the cellular material made from such a phenolic polymer is usually too brittle. In the investigation these quantitative ratios must be the radicals with the formulas II or IV, which are in the compounds with the formulas I or III are included. The synthesis of phenolic polymers with the formulas I and III is in DE-OS 2,417,182 described. These phenolic compositions useful in the present invention consist generally of the phenolic Polymer of the formula I or formula III, together with a compound of the formula V.

The compound of formula V can be used in the phenolic compositions be contained in widely varying ratios of compound V to polymeric composition, however generally in a weight ratio of from 1:30 to 1: 2 and preferably from 1:20 to 1: 5. Examples of suitable compounds of formula V include: m-cresol, m-chlorophenol, m-nitrophenol, 3,5-xylenol and phenol, i.e. hydroxybenzene. Phenol is because of low price, easy accessibility and high reactivity the most preferred compound with the formula V. The phenolic polymers of the formula I and formula III are obtained according to the invention by adding certain reactants in a two-stage process, as described in DE-OS 2,417,182 is to be implemented together.

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In general, anyone can use the method according to the invention any aldehyde can be used to produce useful phenolic polymers. Examples of suitable ones Aldehydes include furfural, benzaldehyde and acetaldehyde. The preferred aldehyde is formaldehyde. Formaldehyde can come in many different ways Forms, e.g. as a 37% aqueous solution (formalin) can be used. However, it is generally required that remove water introduced by the formalin from the polymeric material. Preferably formaldehyde is in the form of paraformaldehyde used, which contains much less water.

The cellular material according to the invention is obtained by simply reacting the phenolic polymer of the formula I or formula III containing alkylol groups and the compound with the formula V under such conditions that a cellular product is formed. As is known in the art of phenolic resin foams, the reaction can be carried out in the presence of a foaming catalyst, a blowing agent and a surfactant. The reaction can be carried out at atmospheric pressure at temperatures between 10 and 50 ⁰ C, preferably 15 and 25 ° C and conveniently.

The cellular materials according to the invention generally have a thermal conductivity (k value) of 19 to 57, preferably 19 to 38 kcal / h / m / ° C / m (0.1 to 0.3, preferably 0.1 to 0.2 BTU / sq.ft Hr- ° F / inch) measured at 24 ⁰ C. the k value is measured on a model 88 tester of ANACON COMPANY.

The fragility of the cellular material is 20% or less. Brittleness is the susceptibility of the foam material to breakage; it is expressed in% weight loss, and they is determined in the 10 minute ASTM C-421 Fragility Test.

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In the process according to the invention, any desired catalyst, which promotes networking and foaming, can be used. However, the preferred foaming catalysts are aromatic Sulfonic acids, including benzene sulfonic acid, toluene sulfonic acid, Include xylene sulfonic acid and phenol sulfonic acid. phosphoric acid can also be used either alone or in admixture with the sulfonic acids. The preferred sulfonic acid is a mixture of equal parts by weight of toluenesulfonic acid and xylenesulfonic acid (see also US Pat. No. 3,458,449). Another foaming catalyst, which has given excellent results so far is a mixture of toluenesulfonic acid, phosphoric acid and water in a weight ratio of 35-50: 50-35:15.

The catalyst is generally used in the minimum amount which give the reaction mixture the desired creaming times of 10 to seconds and hard times of 40 to 500 seconds. in the in general, however, the catalyst makes up from 0.5 to 20, preferably from 1.0 to 15% by weight of the cellular material.

Any propellant which has hitherto been used in known, similar products can be used in the compositions according to the invention (see also US Pat. No. 3,968,300). In general, these blowing agents are liquids at atmospheric pressure, a boiling point between - and 50, and have +100 ⁰ C preferably between O ⁰ C and 5O ⁰ C. The preferred liquids are hydrocarbons or halogenated hydrocarbons. Examples of suitable propellants include chlorinated and fluorinated hydrocarbons such as trichlorofluoromethane, CCl ₂ FCClF ₂ / CCl ₂ FCF ₃ , diethyl ether, isopropyl ether, η-pentane, cyclopentane and 2-methylbutane. The preferred propellants are combinations of trichlorofluoromethane plus 1,1,2-trichloro-1,2,2-trifluoroethane. The blowing agents are used in sufficient quantities so that the resulting foam has a density that is generally between 0.008 and

3 0.16, preferably between 0.016 and 0.08 g / cm (0.5-10, preferably 1-5 pounds per cubic foot). The propellant

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generally makes up 1 to 30, preferably 5 to 20% by weight of the Composition from. If the propellant has a boiling point at or near ambient temperature, it will become blended kept under pressure with the other components. But it can also be kept at temperatures lower than room temperature until it is mixed with the other components.

The cell stabilizing surfactant used in the Any of the hydroxyl group-containing surfactants can be used for the process of the invention be with branched, nonionic structure, which are conventionally used for the production of plastic foams, and whose hydroxyl groups have been blocked. A cell stabilizing surfactant is one such agent that prevents a foam material from collapsing and tearing. Typical surfactants have hydroxyl numbers in the range from 60 to 100. In other words, any conventional branched surfactant whose hydroxyl number is reacted with a suitable blocking agent "such as an organic one Acid, an acid anhydride, acid chloride, acyloxy chloride or alkyl or aryl isocyanate to a value below 50 and preferably has been reduced below 10 is a suitable surfactant Middle. Alcohols can be converted to ethers, but this generally does not lead to a surface-active agent, that acts like a cell stabilizer. The hydroxyl number is determined according to ASTM test D 1638.

The preferred surfactant is the blocked reaction product of an alcoylated amine of Formula VI (Figure 6), in which R is an alkoxylated chain of the formula VII, η is an integer from 2 to 10 inclusive and the ratio p: q at 15:85 to 85:15, with a copolymerizable mixture of dialkyl maleate and N-Viny1-2-pyrrolidone or N-vinyl-Capro lactam, wherein the alkyl radical of the maleate has 1 to 5 carbon atoms. The preferred dialkyl maleate is dibutyl maleate.

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The alkoxylation is performed using a mixture of Ethylene oxide and propylene oxide are carried out at a ratio of from 15:85 to 85:15 and preferably from 20:80 to 60:40. That The molecular weight of the alkoxylated amine is between 1500 and 6000 and preferably between 1800 and 2800. If the molecular weight of the alcoylated amine is less than 1500, the resulting foam collapses. An alkoxylated amine with a molecular weight above 6000 is too viscous to process.

The preferred molar ratio of dibutyl maleate to N-vinyl-2-pyrrolidone is 1: 1, and the mixture of dibutyl maleate and N-vinyl-2-pyrrolidone makes up from 5 to 40% by weight, preferably 20% by weight of the reaction mixture. If less than 5% is used, is the surfactant becomes ineffective if more than 40% is used the foam collapses. N-vinyl pyrrolidone and N-vinylcaprolactam are in equivalent amounts to each other interchangeable, but N-vinyl-2-pyrrolidone is preferred.

The blocking reaction is carried out with a blocking agent. Suitable blocking agents include lower alkyl monocarboxylic acids with 1 to 10 carbon atoms, such as acetic acid, propionic acid, butyric acid, hexanecarboxylic acid, octanecarboxylic acid, Decanecarboxylic acid, isomers of these acids, anhydrides of these acids, acid chloride derivatives of these acids and mixtures of the compounds mentioned. Acetic anhydride is readily available and convenient to use. Aromatic acids, anhydrides and chlorides can also be used. Benzoyl chloride and substituted derivatives thereof such as 3,5-dinitrobenzoyl chloride are examples of this. Alkyl and aromatic isocyanates can also be used. Such factors as solubility in the surfactant and the solubility of the blocked surfactant in the particular phenolic resin are decisive for which system the specialist chooses,

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around the desired closed-cell, stabilized foam to obtain. Examples of suitable blocking agents are acetic acid, acetic anhydride, acetyl chloride and 3,5-dinitrobenzoyl chloride, which have been implemented in such a way that d ^ s surfactant has a hydroxyl value less than 50 and preferably less than 10. The preferred blocking agent is acetic anhydride.

Produce the preferred surfactants of the present invention a uniform, fine-celled foam. The uniformity of the cells is determined by visual and microscopic Investigation. The surfactants must produce a fine cell foam. This property is tested by mixing 2 to 5% surfactant with the phenolic composition and applying a foam to that described Way is generated. Interestingly, there is a low surface tension of the surfactant in the phenolic resin not a prerequisite for achieving a good foam.

The average cell diameter should be less than 0.2 mm and preferably 0.1 mm (ASTM D-2842). Fine-cell foams can be made into closed-cell foams by the method according to the invention. The propellant is then trapped in the cells. The presence of propellants in the cells can be detected using the k-factor drift. Unblended cellular materials containing fluorocarbon gases have an initial k value of about 0.1-0.2 at 24 ^° C. This low value increases over the course of a month or sometimes a few days. The change is known as the k-factor drift. The k-factor is measured at an average temperature of 24 ^° C. The value is determined again at certain time intervals up to about 1000 days. A material that exhibits rapid k-factor drift will achieve a k-factor (BTU / hr / ° F / ft ² / inch thickness) of at least 0.2 in 25 days. A material with

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slow k-drift can take anywhere from 200 days to over two years to reach a value of 0.2. Each Material with a k-value below 0.2 has a high thermal resistance. Of course, the longer it is, the longer the useful life of an insulation material or a lower one Maintains value.

Ball, Hurd and Walker have made extensive studies of k-factor changes ("The Thermal Conductivity of Rigid Urethane Foams", J. Cellular Plastics, March / April 1970, pp.66-78). F. Norton ("Thermal Conductivity and Life of Polymer Foams", J. Cellular Plastics, January 1967, p.23-37) has shown that the diffusion of fluorocarbon gases from unblended foam and the penetration of air into the foam increase the k factor causes. A foam with a slow k-value drift is one that reaches a k-factor of ^{0.15-0.17 after 200-400 days at 24 °} C. and then below a value of 0.2 for the duration of Stays for 5-10 years. Ultimately, all of the fluorocarbons diffuse out of the foam, leaving behind a closed-cell material that only contains air in the cells.

The k-factor of a closed-cell material in the density range

3 *
from 0.032 - 0.048 g / cm / which only contains air is in the

On the order of 0.22-0.26 BTU / hr / ° F / ft / inch thickness at 24 ⁰ C. Therefore, if a foam has a k-factor greater than 0.2 after a short period of time (less than 25 days), essentially all of the fluorocarbon has been diffused from the foam and replaced with air. On the other hand, if the k-factor remains below 0.2 for at least 100 days, a significant part of the fluorocarbon gas will remain in the closed cells of the foam despite the ingress of air.

(2-3 lbs / ft ³ )

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It has been found that by blocking the surfactant Means that provides a fine-cell foam, the content of closed cells increases and the initial k-factor is reduced will.

In addition, one gains by blocking and grafting the surface-active substance By means of a fine-cell foam with a high content of closed cells, a low initial k-factor and a slow k-value drift.

The surfactant is applied in an amount such that that it has a cell stabilizing effect. In general, the surfactant makes up 0.05 to 10, preferably 0.1 to 6% by weight the composition. If too little surfactant is used, the foam will not be stabilized, and too much will be used surface-active. Agent is not only a waste, but can also be used with relatively high surfactants Surface tension (about 35 dynes / cm) lead to a coarser cell structure as a result of cell fusion, so that the foam collapses can. Highly branched, nonionic, blocked, grafted surfactants are preferred.

The above-mentioned alkyl, aryl, aralkyl and / or alkaryl groups can be replaced by one or more groups which do not significantly affect the physical or chemical properties of the surfactant. Examples of substituents include -F, -Cl, -Br, -CH ₃ and -NO _2. In FIG Invention is located. FIG. IX shows a building board 20 with two cover layers 21 and 22 on each side of a cellular material 23.

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Any customary cover layer material can be used to produce building panels according to the invention. Examples Suitable cover materials include kraft paper, aluminum and asphalt-impregnated felt, as well as laminates made of two or several of these substances.

The invention is illustrated in more detail by the following examples; In these examples, all parts and percentages are by weight, unless otherwise stated is. These non-limiting examples describe the invention preferred embodiments of the invention:

example 1

This example illustrates the synthesis of one that can be used in accordance with the invention phenolic polymer of the formula I when using a ratio of phenol to o-cresol of 2: 1.

component (93.6%) Meng e mole , 69 component o-cresol (50%) Gram 98 A. Paraformaldehyde 10580 148 B. Sodium hydroxide 4743 3 , 75. C. phenol 295 196 D. Paraformaldehyde 18428 247 E. Glacial acetic acid 7919 3 F. 225

Components A and B are placed in a reaction vessel. Component C is added over a period of 15 minutes, the temperature rising ^{to 100 ° C. as a result of an exothermic reaction;} it is held at this level for one hour. Components D and E are then added and the temperature is kept ^{at 80 ° C. for four and a half hours.} Finally, component F is added and the reaction product is referred to as resin B.

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The resin B has a viscosity at 25 ^° C. of 29500 cps, a free phenol content of 8.1%, a free water content of 9.1%, a free formaldehyde content of 0.6% and a free o-cresol content of less than 0 ,1 %.

Example 2

This example illustrates the synthesis of one which can be used in accordance with the invention phenolic polymer of the formula I when using a phenol: o-cresol ratio of 4: 1.

The following amounts of the named ingredients are as indicated implemented together.

amounts

component component (93.5% HCHO) Gram mole A. o-cresol (50% NaOH) 6901 63.9 B. Paraformaldehyde 3133 97.7 C. Sodium hydroxide 215 2.69 D. phenol (% NaOH) 24025 255.5 E. Paraformaldehyde 11350 354.1 F. Sodium hydroxide 215 2.69 G Glacial acetic acid 350 5.8.

Components A and B are placed in a reaction vessel. Component C is added over the course of 15 minutes, the temperature rising ^{to 100 ° C. as a result of an exothermic reaction;} it is held at this altitude for 1.5 hours. Components D, E and F are then added, and the temperature is kept ^{at 80 ° C. for 5 hours.} Component G is then added and the reaction product is referred to as Resin C.

Resin C has a viscosity at 25 ° C of 24,300 cps, a free one Phenol content of 8.6%, a free water content of 10.0%, a free formaldehyde content of 2.3% and a free o-cresol content of less than 0.1%.

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Gram mole 800 (0.31) * 64 0.577 136 0.596 4th 0.02439 2 0.01031

Example 3

This example illustrates the synthesis of a surfactant precursor.

Quantities component component

A ethoxylated-propoxylated

Ethylenediamine (Tetronic 704)

B N-vinyl-2-pyrrolidone

C dibutyl maleate

D azo-bis-isobutyronitrile

E tert-butyl perbenzoate

The Kompoennte A is placed in a reaction vessel at 90 ⁰ C. Component B is placed in a dropping funnel. Components C, D and E are mixed together and added to a second dropping funnel. The contents of both dropping funnel are added for one hour at the same time into the reaction vessel, while the temperature is kept at 9O ⁰ C. ^{The temperature is raised to 140 °} C. for a further hour, the precursor of a surface-active agent being formed.

Component A has a molecular weight of 2,600 and a weight ratio of ethylene oxide to propylene oxide of 40:60 and is available from BASF Wyandotte Corporation under the trade name "Tetronic 704".

Example 4

This example illustrates the blocking of the invention useful surfactants.

Quantities component _{r i} Ingredient gram mole

A surfactant precursor 400 0.154

Agent according to example 3

B acetic anhydride 30 0.294.

* JWRC Progress Report, Project No. 05-01-03-09, page 12 "7.28 χ 10" ⁴ moles OH / g ".

800 χ 7 _f 28 10-4 = (ο ν // χ last line.

SZ2 V- Κ ° 'ί OH) J'

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Components A and B are mixed with one another at room temperature and ^{heated to 100 °} C. for 2 hours, resulting in a surface-active agent which can be used according to the invention and which is referred to as “surface-active agent A”.

Example 5

This example illustrates the synthesis of one in the erfindungsge MAESSEN Process usable foaming catalyst.

The following components are combined in the specified amounts in the manner described to give Catalyst A:

Ingredients quantity

Gram 333 333 333

The components A, B and C are mixed. The resulting composition is called Catalyst A.

The following amounts of the following components are mixed in the manner described to give Catalyst B:

Ingredients quantity

Component Description Gram A ULTRA TX 667

B water 333

Components A and B are mixed. The resulting composition is called catalyst B. ULTRA TX is a mixture of equal parts by weight of p-toluenesulfonic acid and xylene sulfonic acids, which is sold by Witco Chemical Company.

component description A. p-toluenesulfonic acid B. Xylene sulfonic acids C. water

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Example 6

This example illustrates the synthesis of a foam based on 2: 1 phenol / o-cresol resoles according to the invention.

Component part . Gram

A resin B 300

B CFCl ₃ 22.5

C CCl ₂ FCF ₂ Cl 22.5

D surfactant A according to FIG. 15

Ex. 4

E catalyst B 40.

Components A to E are mixed with one another in an open vessel for 15 seconds. The mixture is then made into a square Poured cardboard box 30 χ 30 cm and 13 cm high. One Foaming reaction occurs. After a time of about 240 to The material has solidified for 300 seconds. The box with its contents is for a time from 10 min to an hour at 55 to 75 ° C placed in an oven.

" Example 7-12

The procedure of Example 6 is followed with different surfactants Means repeated. The characteristics of the surfactant and the resulting foam are shown in Table I. reproduced.

The "TETRONIC" range of alkoxylated amines is available from BASF Wynadotte Corp. available.

Compressive strength measurements are made in accordance with ASTM D-1621. The oxygen index value is measured according to ASTM D-2863-74. A typical foam has the following properties:

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% 2 , 4 lbs / ft ³ 2857060 O , 120 BTU / hr- 12th % ° F-ft ² / inch 30th psi 34

density

Thermal conductivity
brittleness
Compressive strength
Oxygen index value

Figure X is a graph showing the k-factor against the log. the time is plotted. The k-values are on the y-axis (linear scale) and the time on the x-axis (logical scale) applied as described in Ball, Hurd and Walker (loc.cit).

Materials with a rapid k-value drift reach k-values above 0.2 very quickly, as curve 1 shows, which is typical for example 8 in Table I. After the k-factor reaches a value of 0.22 the rate of increase slows down and tangentially approaches the value 0.26.

Materials with slow k-value drift achieve k-values of less than 0.2 after 1000 days, as curve 2 in Figure X shows, which is typical of Example 6 in Table I.

It should be noted that these k values for 2.5 cm thick uncovered, unlaminated foam sheets apply. Products with top layers have better properties, depending on the permeability of the covering material and all of the free edge surfaces.

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Ζ0

1 1 Tabel I. 704 3 1-phenol / o-cresol- 5 y 6th 120 4th properties Example no. Example no. of phenolic foams from 2: 702 Initially k value
(Btu / hr-F-ft ² / inch) 128 relationship Resins 6th 504 0. * p: q 6th 7th 702 Copolymer content 0. 128 40:60 7th 8th 704 (Weight? 128 20:80 8th 9 2 702 20th 0. 13th 40:60 9 10 Alkoxylated amine 704 20th 0. 128 20:60 10 11 Tabel 20th 0. 40:60 11 12th Tetronic 30th I (port setting) 0. 20:80 12th Tetronic 30th of foams made from phenolic 2 40:60 Tetronic 10 properties Tetronic 10 5 : 1-phenol / o-cresol- Resins Tetronic Density o
(lbs / ff ³ ) Tetronic 2.4 7th Tetronic 2.3 2.3 2.3 ■ k-value drift 2.7 6th 2.6 5 2.6 30th 9 9 24 9

* 0.44 on p. 34 of the JWRC report

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Example 13

This example explains the production of a foam on the Base of a 4: 1 phenol / o-cresol resole according to the invention.

Component part gram

A. Resin C 300 B. CFCl ₃ 22.5 C. CFCl ₂ CF ₂ Cl 22.5 D. Surface active agent A according to 15th Example 4

E catalyst B 35.

Components A to E are mixed with one another in an open vessel for 15-20 seconds. The mixture is then made into a square Poured cardboard box 30 χ 30 cm and 13 cm high. A foaming reaction occurs. After a time of 300-400 sec the material solidifies. The box and its contents are placed in an oven at 55-75 ° C for 10 minutes to 1 hour.

Example 14-16

The procedure of Example 6 is repeated using various surfactants. The characteristics of the surface-active Table II shows the mean and the resulting foam.

A typical foam has the following properties:

density 2.2 lbs / ft ³ Thermal conductivity 0.13 ftu / hr brittleness 32% Compressive strength 25 psi Oxygen index value 40.

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Table II

Properties of phenolic foams made from 4; 1-phenol / o-cresol resins

Example No. Alkoxylated Amine Copolymer Content Ratio p: q

(Wt%)

14 Tetronic 704 20 40:60

15 Tetronic 704 20 40:60

16 Tetronic 702 20 20:80

Table II (continued)

Properties of phenolic foams made from 4: 1 phenol / o-cresol resins

Example No. Density, Initial K Value K Value Drift Catalyst (lb / ft), (Btu / hr- ° F-ft2 / inch) dK , _nn 3. B phr

dLogt ^{vx IU} '

9 11.7 5 13.3 5 11.7

14th 2 .2 0. 13th 15th 2 .3 0. 13th 16 2 .3 0. 12th

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Claims (18)

withdrawal : Synthetic resin foam material made from the reaction product A. Phenolic resin forming reactants B. a propellant and C. A surfactant consists / which blocked the The reaction product is off I. an alkoxylated amine of the formula VI, in which (a) R is an alkoxylated chain of the formula VII, (b) η is an integer from 2 to 10 inclusive, and (c) the ratio p: q is 15:85 to 85:15, and II. A copolymerizable mixture of a dialkyl maleate and N-vinyl-2-pyrrolidone or N-vinylcaprolactam. 2. Foam material according to claim 1, characterized in that the the reactants forming the phenolic resin are phenol and an o-cresol / phenol block copolymer. 030604/0012 3. Foam material according to claim 2, characterized in that the ratio of phenol to o-cresol in the phenolic resin is 1: 1.5 to 10: 1. 4. Foam material according to claim 1, characterized in that the surfactant has been blocked by acetic anhydride 5. Foam material according to claim 1, characterized in that the surfactant has a hydroxyl number less than 50. 6 .. foam material according to claim 1, characterized in that it contains the propellant in sufficient amount to have a density of 0.5 to 10 pounds per cubic foot. 7. Foam material according to claim 1, characterized in that the propellant makes up 1 to 30 wt .-% of the foam material. 8. Foam material according to claim 1, characterized in that the surfactant from 0.05 to 10% by weight of the foam material matters. 9. Foam material according to claim 1, characterized / that the alkoxylated amine has a molecular weight between 1500 and
6000 has. 10. Foam material according to claim 1, characterized in that this copolymerizable mixture blocked 5 to 40 wt .-% of this Reaction product. 11. Foam material according to claim 1, characterized in that this dialkyl maleate has alkyl radicals with 1 to 5 carbon atoms. 030604/0012 12. Foam material according to claim 1, characterized in that it consists of the reaction product of: A. an alkylol group-containing phenolic polymer of formula I in which (a) R stands for HIGH, hydrogen or a radical of the formula II stands, R ⁴
2 (b) the R radicals independently of one another from lower alkyl residues, phenyl residues, benzyl residues, halogen atoms, nitro ■ groups or hydrogen atoms exist, (c) the R radicals independently of one another HOCH-, hydrogen- / 4 are atoms or radicals ß of formula II, R 4 (d) the R radicals independently of one another are lower alkyl radicals Hydrogen atoms, phenyl, benzyl or furyl groups are, (e) χ is an integer from 2 to 10 inclusive, and (f) the phenolic polymer has a molecular weight between 200 and 2000, B. a compound of formula V, wherein the weight ratio of B: A is between 1:30 and 1: 2, (C) a propellant in a suitable amount, as well as (D) a surfactant which is the reaction product is off (I) an alkoxylated amine of formula VI in which (a) R is an alkoxylated chain of the formula VII, (b) η is an integer from 2 to 10 inclusive, (c) the ratio p: q is 15:85 to 85:15, and (d) the molecular weight of the alkoxylated amine is between 1500 and 6000, (II) a copolymerizable mixture of a dialkyl maleate and N-vinyl-2- pyrrolidone or N-vinylcaprolactam, as (III) a blocking agent, namely acetic acid, acetic anhydride, Acetyl chloride or 3,5-dinitrobenzoyl chloride such that the surfactant has a hydroxyl number below ten. 030604/0012 13. Foam material according to claim 1, characterized in that it consists of the reaction product of: A. a methylol group-containing phenolic polymer of formula III ', in which (a) R for HIGH -, hydrogen atoms or a residue of Formula IV stands, (b) the R radicals independently of one another HOCH ^ radicals, Are hydrogen atoms or radicals of the formula IV, (c) χ is an integer from 3 to 6 inclusive, and (d) the phenolic polymer has a molecular weight between 300 and 1,500. B. phenol, where the weight ratio B: A is 1:20 to 1: 5, C. a propellant in a suitable amount, as well as D. a surfactant which is the reaction product of: I. an alkoxylated amine of the formula VI, in which (a) R is an alkoxylated chain of the formula VII, (b) η is an integer from 2 to 10 inclusive, (c) the ratio p: q is 20:80 to 60:40, and (d) the molecular weight of the alkoxylated amine is between 1800 and 2000, II. A copolymerizable mixture of a dibutyl maleate and N-vinyl-2-pyrrolidone, the copolymerizable Mixture makes up 20% by weight of the reaction product and the molar ratio of dibutyl maleate to N-vinyl-2-pyrrolidone 1: 1 as well III. Acetic anhydride such that the surfactant has a hydroxyl number less than 10. 14. Process for the production of a closed-cell foam material, characterized in that a phenolic resin foam forming reactants in the presence of a propellant and a surfactant reacts with one another, which the blocked reaction product is from: 030604/0012 I. an alkoxylated amin of the formula VI, in which (a) R is an alkoxylated chain of the formula VII, (b) η is an integer from 2 to 10 inclusive, and (c) the ratio p: q is 15:85 to 85:15, and II. A copolymerizable mixture of a dialkyl maleate and N-vinyl-2-pyrrolidone or N-vinylcaprolactam. 15. Process for the production of a closed-cell foam material, characterized in that a phenolic resin foam-forming reactants in the presence of a blowing agent and of a surfactant which is the reaction product I. an alkoxylated amine of the formula VI, in which (a) R is an alkoxylated chain of the formula VII, (b) η is an integer from 2 to 10 inclusive, (c) the ratio p: q is 20:80 to 60:40, and (d) the molecular weight of the alkoxylated amine is between 1800 and 2800, II. A copolymerizable mixture of dibutyl maleate and N-vinyl-2-pyrrolidone, the copolymerizable mixture Makes up 20% by weight of the reaction product and the molar ratio of dibutyl maleate to N-vinyl-2-pyrrolidone is 1: 1, as III. Acetic anhydride such that the surfactant has a hydroxyl number below 10. 16. Coated building board with at least one top layer, thereby characterized in that it consists of a closed-cell foam material according to claim 1. 17. Surface-active agent, characterized in that it is the blocked reaction product of: I. an alkoxylated amine of the formula VI, in which (a) R is an alkoxylated chain of the formula VII, 030604/0012 (b) η is an integer from 2 to 10 inclusive, and (c) the ratio p: q is 15:85 to 85:15, and II. A copolymerizable mixture of a dialkyl maleate and N-vinyl-2-pyrrolidone or N-vinylcaprolactam. 18. Surface-active agent, characterized in that it is the reaction product of: I. an alkoxylated amine of the formula VI, in which (a) R is an alkoxylated chain of the formula VII, (b) η is an integer from 2 to 10 inclusive, (c) the ratio p: q is 20:80 to 60:40, and. (d) the molecular weight of the alkoxylated amine is between 1800 and 2800, II. A copolymerizable mixture of dibutyl maleate and N-vinyl-2-pyrrolidone, the copolymerizable mixture Makes up 20% by weight of the reaction product and the molar ratio of dibutyl maleate to N-vinyl-2-pyrrolidone is 1: 1, as III. Acetic anhydride such that the surfactant has a Has hydroxyl number below 10. 030604 / Ό012