United States Patent [19] 

Finaz et al. 

[54] METHOD OF PRODUCING A CELLULAR 

RESIN SUITABLE FOR USE AS AN 

INSULATING MATERIAL 

[75] Inventors: Gilles Finaz; Robert Michon; Michel 

Rasclard, all of Lyons, France 

[73] Assignee: Societe d' Application et de 

Developpement de Techniques 

Nouvelles, S.A.D.E.V., Villeurbanne, 

France 

[21] Appl. No.: 533,859 

[22] Filed: Sep. 20, 1983 

[30] Foreign Application Priority Data 

Sep.20, 1982 [FR] France ................................ 82 16071 

[51] Int. Cl.3 ......................... C08J 9/02; C08G 18/48 

[52] U.S. Cl ....................................... 521177; 5211121; 

5211131; 5211180 

[58] Field of Search .................. 5211180, 121, 131,77 

[56] References Cited 

U.S. PATENT DOCUMENTS 

2,911,380 11/1959 Doedeus ............................. 521/180 

[11] Patent Number: 

[45] Date of Patent: 

4,467,051 

Aug. 21, 1984 

3,047,518 7/1962 Doedeus et al. .................... 521/180 

3,128,258 4/1964 Doedeus et aI ..................... 521/180 

3,274,157 9/1966 Doedeus et al. .................... 521/180 

3,311,573 3/1967 Graham et al. ..................... 521/180 

3,311,574 3/1967 Bowering et al. .................. 521/180 

3,311,575 3/1967 Graham et a1. ..................... 521/180 

3,415,763 12/1968 Sonnabend .......................... 521/180 

OTHER PUBLICATIONS 

Article: Development of a Canadian Standard for Urea 

Formaldehyde Thermal Wall Insulation, Thermal Insulation Performances, ASTM STP, 718-1980, pp. 

361-394, (Bowles & Shirliffe). 

Primary Examiner-Morton Foelak 

Attorney, Agent, or Firm-Karl F. Ross; Herbert Dubno 

[57] ABSTRACT 

A cellular foam particularly suitable for use as thermal 

or accoustic insulation is produced by the condensation 

in an acidic medium in the presence of a catalyst hardener of methyloldihydroxydiphenylmethylene ether 

isomers. 

15 Claims, No Drawings 
1 

4,467,051 

METHOD OF PRODUCING A CELLULAR RESIN 

SUITABLE FOR USE AS AN INSULATING 

MATERIAL 

FIELD OF THE INVENTION 

Our present invention relates to a method of producing a cellular or foamed synthetic resin composition 

resin composition and to the composition which thus 

results and especially to the use of the composition as an 

insulating material. More particularly, the invention 

relates to cellular or foamed compositions obtained by 

the condensation of isomers of methyloldihydroxydiphenylmethylene ether. 

BACKGROUND OF THE INVENTION 

5 

2 

D. L. McElroy and R. P. Tye, Editors, American Society for Testing and Materials, 1980, pp 361-394. The 

description of these publications can be found on page 2 

of the French text. 

These studies have concluded that the shrink~ge can 

be up to about 21% by volume and it can be estimated 

that such shrinkage ,reduces the thermal performance of 

the material by 60% with respect to the same material 

hypothetically filling the original space without shrink10 age. 

These undesirable 'results have been confirmed by 

numerous experiences carried out utilizing urea-formaldehyde foams. 

One might expect the polyurethane foams to effec15 tively replace the urea-formaldehyde foams because of 

their excellent thermal pll'Operties, their desirable meIt is common to provide insulation for buildings, chanical properties, 1m!! theil!' good dimensional stabilespecially residences, and transport vehicles (land vehi- ity. 

cles, maritime vehicles and aircraft), and for indus,trial In practice, however, it ill fm,md that this ie not the 

structures such as ducts, utilizing cellular synthetic resin 20 case. For example, it is not possible or mdvantageous to 

insulating compositions which generally are applied in simply inject such materials in the space between a wall 

the form of a liquid foam which reacts and hllll'dens to and a partition because of the sharp increase in pressure 

produce the cellular product. which occurs when this material is injected into III wall. 

The reaction can be carried out in a factory by treat- The expaillsion pressure of the foam appears to be of the 

ing the industrial structure tobe insulated or at the site 25 order of kg/cm2 and the use of such materials require 

in the case of building structures, either by casting the support for the walls of the cavities into which the 

reactive liquid composition in a space to be provided polyurethane foam is introduced. 

with the insulating material, by injection of the reactive For example, if a metallic structure is filled in the 

liquid into a cavity to be filled thereby, or by projecting factory with such foams, the metal panels frequently are 

the composition against a surface to be coated, Gener- 30 distorted. Sandwich structures likewise formed with 

ally speaking these liquid reactive compositions have 

been urea-fonnakllehyde resins, polyurethane resins, such foams are also distorted or deformed. If the polyepoxy resins or phenol-aldehyde (phenol-formalde- urethane resin is injected between a supporting wall and 

hyde) resins or combinations thereof. a partition, the partition is frequently displaced, cracked 

Because of the simplicity of application, urea-for- 35 or otherwise ruptured in a wholly unacceptable manmaldehyde resins Ilave been widely used for over 20 nero years in Europe and North America for the insulation of Of course, one can utilize specially reinforced partiprivate domiciles and other structures. tions and other structures adapted to withstand the 

Generally the reactive composition is discharged expansion pressures of polyurethane but, of course, this 

from a machine which proportions the two components 40 can only be done with loss of economic advantages of 

in a fixed ratio with respect to one another, e.g. a 50/50 the polyurethane foam. 

proportion by volume. The supply reservoirs of the Furthermore, the polyurethane foams cannot be utimachine thus can contain the two components, one of lized effectively in existing structures without such 

which is the resin in the form of an aqueous solution of reinforcements. 

a precondensate of urea-formaldehyde containing a 45 Polyurethane fomus suitable for application by proplasticizer. The other composition can be an aqueous jection onto a surface have also been developed, for 

solution of the catalyst and the foaming agent which example, for insulating terrace roofings, albeit with the 

can include an anionic surface active agent in an acid disadvantages discussed above. Furthermore, the moismedium. The two components are mixed, foamed in the ture in concrete or support structures against which the 

presence of air and the resulting composition, in the 50 polyurethane foam may be brought, tends to affect the 

form of a cream having the consistency of shaving hardening or setting of the resin. In the region where 

cream, can be cast between slabs, can be injected the foam contacts the support, the properties of the 

through small holes in the space between partitions and foam differ from those elsewhere. 

walls, or can be coated onto structures to be provided Another difficulty frequently encountered in the use 

with insulating layers. 55 of polyurethane foams is the limited temperature at 

The foam hardens in about one minute to leave a which it can be applied, namely, between 10· and 30· C. 

cellular material. Thus in severe temperature extremes as may occur in 

Initially the density of the foam depending upon the the summer and in the winter, the use of polyurethane 

humidity, is about 40 to 48 kg/m3 but after drying over foams is drastically limited. 

a period of several days to several weeks, the density 60 Yet another disadvantage of using polyurethane 

diminishes to a level between 10 and 13 kg/m3. Regret- foams is the flammability characteristics thereof, a distably, significant shrinkage accompanies this reduction advantage which is also found with urea-formaldehyde 

in density and drying and is responsible for a significant foams. 

loss in thermal insulating performance of the material. The conventional polyurethane foams are somewhat 

An extensive study of this subject can be found in 65 flammable and cannot be utilized where there is a danBowles and Shirliffe: Development of a Canadian Stan- ger of ignition. This is especially the case in buildings 

dard for Urea Formaldehyde Thermal Wall Insulation, and domiciles and for the insulation of roof, ceiling and 

Thermal Insulation Performances, ASTM STP 718 and like structures when sandwich panels are provided. 
3 4,467,051 

4 

Naturally, various remedies to this problem have minute. With resol resins, while it is possible to modify 

been developed and, for example, some firms have fab- the reactivity. by various means, e.g. controlling the 

ricated polyols for use in the production of polyure- concentration of the methylol group, the nature and 

thane foams which enable them to be fire retardant and, concentration of the catalyst and hardener, or other 

for example, to conform to the M 1 class utilizing the 5 aspects of the reaction, it is found that when the duraepiradiation test described in French industrial standard tion of contact is.sufficient for the initial aspect of the 

NF P 92-501. reaction, the exothermicity of the reaction is insufficient 

However, such foams contain nitrogen, chlorine or to provide, at ambient temperature within an appropribromine or combinations thereof and, upon combina- ate time of the order, say, of two minutes, a complete 

tion, emit opaque smoke or highly toxic vapors and 10 drying and hardening of the foam. 

thus, although they are less flammable, upon contact A second disadvantage of resol based resins used to 

with a source of combustion, can give rise to other date is that the viscosity of the resol resin for foaming is 

health disadvantages. generally between 1,000 and 5,000 centipoises. It is 

Epoxy resins have been found to be interesting in the possible to reduce this viscosity to slightly below 1,000 

production of thermally insulating foams, although 15 centipoises by increasing the concentration of water in 

their cost is so great that they have been utilized only the product but this reduces the reactivity of the resin 

effectively in industrial apparatus such as steam boilers and diminishes the properties of the fmal product as 

of the like, which justify the higher cost. Furthermore, well as its dimensional stability. The viscosities of the 

their combustion characteristics have limited their ap- resol resins which must be used do not permit the generplicability in the same manner as polyurethane foams. 20 ation of light foams of the type which have been found 

Phenol-aldehyde resins, generally referred to as pheno- to be satisfactory with urea-formaldehyde resins and 

lic resins, have the advantage that they are exception- indeed it is generally not possible to obtain a final denally resistant to combustion for materials which are rich sity of the material significantly below 30 kg/m3 even 

in carbon and hydrogen. Indeed, it is possible to form under the best conditions. 

from them foams, which are non-flammable and are in 25 Still another disadvantage of resol-based resins for 

the M 1 class for the epiradiation test as previously the purposes described is the need to utilize large quandescribed. tities of hardening agent or catalyst. Because of the poor 

It is for this reason that considerable effort has been reactivity and the higher apparent density of the foam, 

expended in the development of such foams where it is generally necessary to accelerate the reaction by 

there is a chance of combustion, for example, in building 30 utilizing comparably large quantities of hardening 

structures and in transport vehicles. agents or catalysts. The compounds are generally acids, 

The usual method of producing a foam of a phenolic for example sulfonic acids, and when these are used in 

resin comprises mixing a resin known as a resol with an excess, they tend to increase the hydrophilic character 

acidic compound in the presence of a surface active of the foam and make the same corrosive. 

agent and a blowing agent, permitting the mixture to 35 Yet another disadvantage of the use of resol based 

react under the exothermicity of the reaction until a resins for foam insulation is the limited temperature at 

fluid foam is formed which hardens progressively until which the foam can be generated, generally a temperathe reaction concludes. ture in the range of 10° to. 25° C. Below 10° C., the 

The resol based phenol-aldehyde resins which can be product is difficult to handle and there is a risk that it 

foamed in the manner described can be applied by the 40 will solidify or plug the pumps, piping, nozzles and the 

methods utilized with other resins, e.g. by casting, by mixing head. Furthermore, the reactivity is substanprojection onto a surface and by injection into a cavity. . tially reduced at temperatures below 10° C. 

However, because of a variety of difficulties generally At temperatures about 25° C., the control fo the reacassociated with the formation of a foam of such resins, tion can be lost. Consequently, one is generally limited 

the use thereof has been marginal to date. 45 in the time of application of the product to a narrower 

As a matter of fact, considerable research has gone interval than that which has been found to be disadvaninto the efforts to control the reaction and into the tageous for the use of urea-formaldehyde resins. 

production of articles utilizing such resins without sig- It has also been found that the resol resins of convennificant success. tional types have poor storage stability of shelf life. The 

For example, resol based phenol-aldehyde resins 50 resins tend to condense autogeneously with increase of 

have poor reactivity. When a foamed resin is to be . their viscosity. The reaction occurs more readily as the 

produced from two components, it is necessary to pro- storage temperature increases. Resol resins are individe sufficient time for the two components to react in cated to have shelflives less than several weeks. Consethe mold or in the cavity to be filled or in the device for quently it is difficult to stock the materials at various 

metering the two components into the mold or cavity. 55 locations or to ship them long distances. 

However, this time cannot be excessive because there is Finally, it should be mentioned that the conventional 

always the risk that the mixture will drain from the resol resins produce foamed products which have poor 

cavity, especially if the walls thereof are porous, as is dimensional stability and which are somewhat brittle. 

the case in building structures. For urea-formaldehyde It has already been recognized that the mechanical 

resins, the time required for the reaction is less than one 60 strength propeI1ies of foamed resins formed from such 

minute which has been considered to be a suitable time resols are poor and especially that they have extremely 

period. low tensile strength. 

Within this time period, the foaming reactions should Indeed, when dimensional stability is tested accordbe rapid and hardening should follow directly with a ing to the French standard NFT 56122, i.e. after several 

sufficient exothermicity to completion and to eliminate 65 cycles including a conditioning phase at ambient temvolative materials. perature and in a relatively constant humidity atmoThus the desirable kinetic curve should increase ex- sphere, followed by a period in an oven, it is noted that 

ponentially with temperature after a period of about one there is a substantial dimensional variance. In suitable 
5 

4,467,051 

6 

foams, this variation is minimal. A minimum variation 

under this test is necessary if degredation of the foam 

with time is to be avoided since the test represents an 

accelerated weathering or aging test. In fact, dimensional variations under such tests should be less than 2% 5 

and this value is difficult to guarantee when the foam is 

made of a resol resin of the type described. 

HOCH2-ArOH-[CH2-AROH(CH20H)xJy-H 

in which small x represents 0 or I and thus indicates the 

number of methylol groups which can be substituted on 

the aromatic hydroxy moiety; small y is Ii highly variable integer representing the polymerization of these 

units and generally represents from several units to 

several tens of units. 

OBJECTS OF THE INVENTION The resol resins are thus characterized at a chemical 

It is, therefore, the principal object of the pr~sent. 10 level, by hydroxy aromatic moieties connected to one 

invention to overcome the disadvantages described another· by methylene groups. A certain number of 

above. these moieties can comprise in an ortho or para-position 

A more specific object of the invention is to provide with respect to the phenolic hydroxyl group, with 

a method of making a cellular foam, particularly suit- methylol groups apart from all other reactive functional 

able for insulation purposes, which can be applicable in 15 units. 

situ without any of the disadvantages outlined above in The hardening of the resol resin in the presence of 

connection with resol resins. acid compositions, referred to as hardeners or ~atalysts, 

Still another object of the invention is to provide an is effected by a condensation of the methylol groups 

improved insulating material. with the hydroxy aromatic moieties belonging to the 

DESCRIPTION OF THE INVENTION 20 resin itself or to the hardener. The hardeners are gener- ally aromatic sulfonic acid and can be simple compounds such as the para-toluene sulfonic acid, hydroxybenzene sulfonic acid, etc, or sulfonic resins such as the 

condensate of hydroxy benzene sulfonic acid with formaldehyde. 

These objects and others which will become apparent 

hereinafter are attained, in accordance with the present 

invention which is based upon our discovery that it is 

possible to produce a cellular product wihout any of the 25 

disadvantages of earlier resol based resins by condensing at least one isomer ofmethylol-dihydroxy-diphenyldimethylene ether (MDDME) of the empirical formula 

CisHlS04 and especially the 3-methylol-2,2' -dihydroxydiphenyldimethylene ether of the structural formula: 30 

According to conventional techniques, the hardening 

reaction with the resol resin gives an insoluble and 

non-fusible foam. The latter has a three-dimensional 

reticulate structure with crosslinking of the molecules 

as a consequence of the fact that the number of methylol 

groups per mole of resol resin is greater than unity. 

OH The MDDME is a compound chemically different 

"'~ .COHH2-0. '-.. CH20"'~ CH20H from the products which are condensed in the conven- 35 tional resol resin and produce condensation products 

which are likewise different. 

Firstly, the MDDME is a mixture of isomers of well 

. , defmed structures as represented by the formulas given 

and the 3-methylol-2,4' -dihydroxy-diphenyldimethy- above. By contrast with resol resins, these formulas do 

lene ether of the structural formula: 40 not have any recurrent units and MDDME is readily 

definable by nuclear magnetic resonance spectrometry 

as having a molecular weight of 260. 

Another important distinction is that the MDDME 

has a dimethylene ether group (-CH2-0-CH2) 10-

(possibly in a mixture of the two isomers). 

45 cated between the two aromatic moieties of the compound. The resol resin and its condensate does not contain a corresponding internuclear chain but rather links 

the internuclear moieties by a methylene group which is 

neither reactive nor identical to the ether linkage and 

hence the hardening is effective exclusively by the reaction of methylol groups and the substituted aromatic 

moieties. The hardening kinetics of MDDME also proceed differently. 

According to a feature of the invention, the mixture is 

constituted' primarily by or is constituted of a majority 50 

of the 3-methylol-2,2' -dihydroxy-diphenyldimethylene 

ether. 

We have found that the use of isomers of MDDME 

permits the condensation to form an insulating foam 

which can be applied by casting, injection, projection 55 

and pulverization. 

The transformation of MDDME into a resin can be 

effected in a manner similar to that utilized in generating foams from resol resins and utilizing the same hardening or catalytic agents. However, the chemical com- 60 

position of MDDME, the kinetics .of its reaction, its 

physical characteristics and the properties of the resins 

obtained differ significantly from those of the resol 

resins as will be detailed below: 

The resol resins are polycondensates ':of a hydroxy 65 

aromatic compound such as penol with formaldehyde. 

These resols can be represented by the formula: 

The hardening of the MDDME requires, on the one 

hand, the reaction with a methylol group (a group 

which itself cannot contribute to cross-linking and the 

formation of a network) and, on the other hand, the 

participation of the dimethylene ether group. 

For a better appreciation of the invention, a reaction 

scheme for the hardening of the MDDME is provided 

below. However, the process shown is not exclusive, 

i.e. various other and side reactions may occur depending upon the operating conditions and the reaction' sequence may differ depending upon the nature and concentration of the hardener and the temperature used. 

Consequently, the explanations below as to the nature 

of the hardening of the MDDME should not be considered to be any limitation on the invention. 
7 

4,467,051 

8 

The hardening of MDDME was studied at ambient 

temperature in the presence of acid hardeners which 

generally were identical to those employed for the 

hardening of conventional resol resins. 

which can contain (with a variability of up to, say, 

25%): 

MDDME=75% by weight 

The polycondensation reaction (I) is initiated at the 5 . 

methylol group. This reaction is an ionic reaction and 

Water= 13.5% by weight 

'2,6-dimethylolphenol=5% by weight 

mixture of methylolphenolisomers=4% by weight 

phenol-1.2% by weight its velocity is initially proportional to the concentration 

of hydrogen ion. The methylol group condenses with a 

substituted hydroxyaromatic nucleus with formation of 

a methylene bridge and elimination of one molecule of 10 

water (reaction I below). 

The reaction is accompanied by the release of heat 

which accelerates the decomposition in the acid medium of the dimethylene ether group with formation of 

an internuclear methylene bridge and elimination of a 15 

molecule of formaldehyde (reaction II) belo~. 

The reaction synergism can be manifested by an acceleration of the temperature increase and a vaporization of by-products of the reaction. 

When the dehydration is complete, the ionic reaction 20 

is terminated although the decomposition of the dimethyl ether groups can continue by a free radical reaction. 

The formaldehyde generated by the reactant II has a 

high reactivity during the ionic reaction phase. It con- 25 

denses with two substituted hydroxyaromatic nuclei 

and thus creates a new methylene bridge with elimination of a molecule of water. It participates essentially in 

a cross-linking of the polycondensate (reaction III below). 30 

• H-':H-CH'-r-CH~;::",-cu,OH 

35 

H [-ArOH-cH2-0-cH2-ArOH-CH21n-OH + oH20 

(II) '\ ! 

mineral salts (catalyst residues) = 1 % by weight 

nonidentified impurities=0.3% by weight. 

The MDDME is generally in the form of a mixture of 

the two isomers: 

3-methylol-2,2' -dihydroxy-diphenyldimethylene ether 

and 

3-methylol-2,4' -dihydroxy-diphenyldimethyhme ether. 

These two isomers are generally in a weight proportion of 9 parts of the first to I part of the second. 

The crude products described' above, which is referred to as technical grade MDDME, is a clear liquid 

of an odor resembling that of phenol. Analyses for 

traces of aldehyde found none. The composition can be 

handled in free air without particular risk to the respiratory tract. 

The characteristics of the technical grade MDDME 

are as follows: 

viscosity measured by a Brookfield viscometer at 23° 

C. = 170 to 180 centipoises. 

Density at 25° 'C. d422 = 1.87 glcm2• 

pH of a 10% solution in water=7.4. 

In spite of its high reactivity, the product can be 

stored for several months at temperatures below about 

20° C. and up to about 20° C. without noticeable change 

in viscosity. After two months, the viscosity rises only 

to about 200 to 220 centipoises. 

In order to obtain a foamed composition from the 

MDDME technical grade product, a foaming agent can 

be added which is insoluble and/or we can add a surface-active agent of the emul~ifier class. 

It is desirable 'that the MDDME contain a certain 

H [-ArOH-CH212n OH + 0 CH20 

t 

40 amount of water since this is inlportant for the foaming. 

(III) 

45 

After the ionic step, the nascent formaldehyde released with the water vapor without reacting with the 

polycondensate, is available as a foaming agent to pro- 50 

mote the expansion of the resin. Consequently, the 

transformation of the formaldehyde in cross-linking the 

polycondensate is incomplete. 

The result is a macromolecular reticulate structure 

which is moderately cross-linked and which explains 55 

the particular properties of the cellular resin obtained 

by condensation of the MDDME, namely, high resilience and a dimensional stability much greater than that 

of the resol resins. 

Finally, after the reaction is complete there are no 60 

longer groups available which can generate formaldehyde even when the composition is brought to an ele-' 

vated temperature at which pyrolysis may occur. This 

too contributes to the high stability of the product. 

According to the process of the present invention, the 65 

MDDMEwhich is polymerized and cross-linked is 

used in the form of the crude products obtained in the 

fabrication of the MDDME, namely, a composition 

Naturally this is the case when the technical grade 

MDDME is used. If water is not present, water can be 

added so that the composition to be foamed contains 

between 5 and 20% by weight water. ' 

The foaming agent can be added in an amount of 0.1 

to 12% by weight of the composition to be foamed and 

is advantageously a liquid having a low boiling point. 

Preferred foaming agents include: 

saturated aliphatic hydrocarbons, e.g. petroleum 

ether and other mixtures of hydrocarbons obtained as 

distillation cuts in the fractional distillation of petroleum, the cut having a distillation curve at ambient 

pressure running from 30° to 70° C.; 

aliphatic ethers, for example ethyl ethers. and especially diethyl ether; and 

halogenated hydrocarbons and especially methylene 

chloride and certain freons such as Freon 11 (fluorotri~ 

chloromethane) and Freon 113 (1,1 ,2-trichloro-2,2, I-trifluoroethane ). 

It is also more economical to employ a mixture-foaming agent, for example Freon 113 CM which is a mixture of Freon 113 and methylene chloride. 

The surface active agent is intended to produce a 

stable emulsion of the foaming agent in the aqueous 

solution of the MDDME. It is utilized in a proportion of 

0.01 to 6% by weight of the composition. 

Preferably the surface 'active agents which are used 

are nonionic surfactants because these have no unfavor-
9 

4,467,051 

10 

able effect on the stability of the MDDME .. Of particular value are the nonionic surfactants which are polyethoxy ethers of fatty alcohols, alkyl phenols and 

polysilicones. 

Best results are obtained using mixtures of the surface 5 

active agents prepared such that their hydrophilic-lipophilic equilibrium point or H.L.B. point corresponds to 

Such sulfonic acids can be employed individually or 

in mixtures and can be diluted with phenol to control 

their acidity index and hence their reactivity for foaming and hardening of the MDDME. 

Specific examples of such hardeners include: 

phenol sulfonic acids C6H4(0H)(S03H), particularly in 

the form of mixtures of their isomersj 

the cresolsulfonic acids C6lI3(CH3)(0H)(S03H)j 

the naphthosulfonic acids CloH6(0H)(S03H)j 

the H.L.B point required for emulsifying the foaming 

agent in MDDME containing 5 to 20% by weight water. 

To emulsify the petroleum ether, an emulsifying 

agent composition E can be used whose composition is 

10 the dihydroxydiphenylmethane sulfonic acids 

C6H40H-CH2-C6H3(0H)(S0 3H)j 

as follows: 

the dihydroxydiphenylpropane sulfonic acids 

C6lI40H-C(CH3hC6lI3(OH)(S03H)j condensate of 4 moles of ethylene oxide (E.O.) with 

oleocetylic alcohol-70% by weight, 

nonylpehnol condensate with 4 moles of ethylene 

oxide (E.O.)-lS%, and 

the dihydroxydiphenylbutane sulfonic acids C6lIs(OH15 )-C-(CH3)(C2HS)C6H3(0H)(S03H)j and 

nonylphenol condensate with 9 moles ethylene oxide-1S%. 

The MDDME based foam compositions are foamed 20 

and hardened by the addition of an acid catalyst hereinafter referred to as a hardener. 

Tests have shown that the velocity of the reaction of 

the MDDME is, at least in its initial phase, proportional 

to the concentration of hydrogen ions and it is possible 25 

to utilize as the hardener, those acids whose dissociation 

constant is sufficient to reduce the pH of water to 4 pH 

units and preferably below a pH of 2. 

A significant number of mineral and organic compounds satisfy this requirement and indeed any mineral 30 

or organic acid capable of reducing the pH to a pH of 2 

or lower will suffice. 

Best results are obtained when the acidity of the mixture of the MDDME and hardener is between 0.5 and 2 

pH units. 35 

For the higher pH values, the reaction is slowed and 

it may be necessary to supply heat from the exterior. 

At pH values above this range, the reaction is sharply 

slowed and it may be necessary to provide an external 

heating source to maintain the reaction. 40 

At pH values below this range the reaction becomes 

difficult to control. Within this pH range the foamed 

composition of MDDME foams and hardens at initial 

temperatures between -50 C. and +350 C. which permit the formation of the cellular product by conven- 45 

tional in situ processes for insulating buildings and the 

like. 

Care may have to be taken to avoid a strong acidity 

which may be responsible for hydroscopy and a corrosive character of the cellular resins which are thus pro- 50 

duced. Preferably the acid hardeners act both as catalysts and as polycondensation agents with the 

MDDME, thereby removing them from availability as 

free acids .. Consequently, it is advantageous to utilize 

compositions and reaction conditions such that the 55 

fOaming and hardening are satisfactory but the cellular 

resin contains the least possible amount of free acid 

compounds and particularly free acid compounds' 

which are extractable by water. 

The preferred hardeners are organic sulfonic acids of 60 

the following type: containing one or more aromatic 

nuclei (benzenic, naphthenic) sulfonic acidsj 

containing a phenolic hydroxyl group on at least one 

of thenucleij 

containing one or more sulfonic acid groups on at 65 

least one of the nucleij and' 

containing a hydrocarbon chain CnH2n, where n is an 

integer, for connecting the nuclei. 

the polyhydroxyphenylmethylene sulfonic acids 

H-[C6lI2(OH)(S0 3H)-CH21n-C6H3(0H)(S03H)j 

and 

polysulfonic acids obtianed by partial sulfonation of 

liquid novalac resins. 

The formula of these acids is similarly to the formulas 

given previously but the number of sulfonic groups is 

less than the number of hydroxyphenyl nuclei. The 

liquid novolac resins are themselves obtained by a condensation of phenol with formaldehyde in the presence 

of an acid catalyst and with a molar ratio of phenol:formaldehyde greater than 1. 

EXAMPLE 1 

The foaming composition is obtained by the addition 

to 100 parts by weight of technicai grade MDDME as 

defined previously, of emulsifier E as a surface active 

agent (3 parts by weight) and 8 parts by weight of petroleum ether. The hardener is prepared by mixing 77 parts 

by weight of technical grade phenolsulfonic acid with 

23 parts by weight of crystallized phenol containing 

10% water. Using a turbine stirrer, for especially vigorous agitation, 1000 g of the foamed composition are 

mixed with 250 g of the hardener. After 20 seconds of 

agitation, the mixture begins to foam and assumes the 

appearance of a cream. 

This cream is cast into a cylindrical cavity having a 

volume of 100 1. The foam develops intensively and 

overflows the cylinder. The volatile material is evolved 

in the form of a gas and 3 minutes after mixing of the 

two components and about 2 minutes after expansion 

begins, the foam being hot is totally hardened and dry; 

Samples are cut from the molded body and tests of 

properties are carried out with the following results: 

apparent density: 10.6 kglm3j 

resistance to compression: 0.3 kglcm2j 

dimensional stability according to the French standard NFT 56122: variation less than 1 %j 

thermal conductivity W ImK=0.030j 

fire-retardant tests according to the epiradiation test 

previously described: the material is class Ml. 

The remainder of the block is comminuted in a blade 

grinder to form granules with a particle size between 0.5 

cm and 6 cm. The apparent density of the granules is 8 

to 9 kg/m3. These granules can be filled directly into a 

space to be thermally insulated. 

EXAMPLE 2 

Foamable Composition: 

Technical grade MDDME: 1OO'parts by weightj 

surface active agent of the silicon!! type (DC 193 

marked by Dow-Coming): 2 parts by weightj 
4,467,051 

11 12 

trichlorofluoromethane (Freon 11): 2 parts by 

weight; 

1, 1,2-trifluoro-2,2, I-trichloroethane (Freon 113): 2 

parts by weight; 

orifice to orifice, thereby filling the wall and driving the 

air from the latter. The foaming time requires about 20 

seconds and allows the insulation of 60 m2 of wall with 

a void thickness of 6 cm per hour. This rate has been 

methylene chloride: 2.5 parts by weight. 

Hardener: 

5 found to be extremely satisfactory in practice. 

The hardener is prepared by sulfonation, with 77 

parts by weight of 95% sulfuric acid, of a mixture constituted by 51.5 parts by weight of dihydroxydiphenylmethane and 48.5 parts by weight of phenol. 

Fabrication of Insulating Panels: 

10 

The foaming composition and the hardener are introduced into respective reservoirs of a two component 

machine for applying reactive systems with variable 

volumetric proportions. The ratio of the two compo- 15 

nents is set so that 15 parts by weight of the hardener is 

combined with 100 parts by weight of the foaming 

formulation. The two components are mixed in a dynamic head and are cast in an amount of 4.5 kg of the 

composition into a closed parallelopipidal mold having 20 

dimensions of 3 m Xl m X 0.06 m. 

The casting time is 10 seconds and corresponds for 

the time for delivery of 4.5 kg from the head. After 3 

minutes, the mold is opened and the hardened and nonsticky pannel is withdrawn. 25 

The pannel has the following characteristics: 

apparent volumetric mass (apparent density): 24 

kg/m3; 

resistance to compression: 0.6 kglcm2; 

dimensional stability as measured in the manner de- 30 

scribed: variations less than 1 %; 

thermal conductivity in W /mK: 0.032; 

flammability test: class M1. 

A determination of the combustion and pyrolysis 

products was carried out by burning 1 g of the material 35 

in a quartz tube in a tube furnace at 700° C. while passing a current of air at a constant rate through the tube. 

The gaseous products were 2800 mg of carbondioxide 

gas and 330 mg of carbon monoxide gas. No halogen or 

cyanide was detected. 40 

EXAMPLE 3 

Foaming Composition 

Technical grade MDDME: 100 parts by weight; 

surface active agent Atmer 171 marketed by the Atlas 45 

Chemical Company: 1.5 parts by weight; 

trichlorofluoromethane (Freon 11): 2.5 parts by 

weight; 

1,1,2-trichloro-2,2,I-trifluoroethane (Freon 113): 2.5 

parts by weight. 50 

Hardener: 

The hardener of Example 2: 30 parts by weight; 

phenolsulfonic acid: 20 parts by weight. 

Insulation of Dwelling Walls with Evacuation of Air 

A machine is used of the type for two component 55 

application with a volumetric ratio of 100/30. The two 

components are charged into the reservoir of this machine and are displaced independently via pneumatic 

pumps through a tubular hose of a length of 50 m. At 

the end of this hose, a static mixing piston having air 60 

injection is provided to mix the two components and 

entrain them in an air stream into the wall. 

To permit the evacuation of air within the wall, e.g. 

between a partition and a structural wall, small orifices 

at regular intervals spaced about 1 m are provided along 65 

the wall. At one end of the wall, the end of the gun is 

introduced into the orifices and the mixture is blown 

into the space between the wall. The gun is moved from 

The operation is effective at ambient temperatures 

between -5° C. and +35° C. 

Filling of hollow metallic Structure of a Thickness of 

8 cm for Preparation of a Curtain Wall: 

The technique previously described for the insulation 

of a dwelling wall is used although here the operation is 

carried out in the factory. After filling of the hollow 

metallic wall structure with the cellular resin, no deformation of the metallic structure is noted. 

Roof Insulation 

The formulations of the previous examples are used in 

a machine for injecting the resin into the spaces between 

the joists of a roof. The material is applied against the 

inner surface of the roof to a thickness of 20 cm in the 

single pass. 

The apparent density of the cellular resin measured 

by samples taken from the product show that the product has a density of 18 to 20 kg/m3, depending upon 

thickness; when applied by injection, but about 12 

kglm3 when applied by expansion after-spreading upon 

the roof surfaces. 

EXAMPLE 4 

Foaming Composition: identical to that of Example 3; 

Hardener: identical to that of Example 2. 

Insulation by Spraying of the Foundation of a Building 

The machine described in Example 3 is modified to 

deliver a fixed ratio of the two components at 100/100 

parts by weight. The combination is pulverized and 

sprayed on the basement to produce a cellular resin 

having a thickness of about 3 cm. The foaming and the 

hardening appear practically instantaneously so that 

there is no danger of flow. The apparent volumetric 

mass of the insulating layer varies between 25 and 35 

kg/m3. . 

The compressure resistance of the product exceeds 1 

kg/cm2. 

EXAMPLE 5 

Foaming Composition: that of Example 2; 

Hardener: sulfonated novolac-type Alveophen 76058 

as produced by the SHEBY division of the URACHEM. Group. -

Production of inSulating Panels: 

The ratio between the two components, namely, the 

foamlhardener ratio is 100/20. 

The method used was that of Example 2 and the 

casting time was 16 seconds and corresponded to the 

delivery of a weight of 7.2 kg of the product. The product hardened over a period of 5 minutes. The characteristics of the panel are the following: 

apparent volumetric mass (apparent density): 38 

kg/m3; 

resistance to compression: 1.2 kglm3; 

dimensional stability: variation less than 1 %; 

thermal conductivity inW /mK: 0.034; 

flammability test: class M 1. 

We claim: 

1. A method of producing a cellular resin which 

comprises the steps of condensing at least one methyloldihydroxydiphenylmethylene ether isomer of the empirical formula C1SH1604. 
4,467,051 

13 14 

2. The method defined in claim 1 in which the isomer 

is at least one of the following isomers: 

the 3-methylol-2,2' -dihYdroxY-diphenylmethylene 

ether of the formula: 

or the 3-methylol~2,4' -dihydroxy-diphenylmethylene 

ether of the formula: . 

3. The method dermed in claim 1 wherein said isomer 

on at least one aromatic nucleus, at least one sulfonic 

acid group per molecule. 

S. The method defined in claim 1 wherein the sulfonic 

acid is selected from the group which cOl!lslists of phe5 nolsulfonic acids and isomers thereof, cresolsuhonic 

acids naphthosulfonic acids, dihydroxydiphenylmethane sulfonic acids, dihydroxydiphenylpropane sulfonic acids, dihydroxydiphenylbutane sulfonic acids, 

polyhydroxyphenylmethylene sulfonic acids and poiy10 sulfonic acids obtained by the partial sulfonation of 

liquid novolac resins. 

9. The method defined in claim 1 wherein the condensation is carried out by mixing the catalyst hardener 

and a foaming composition containing methylol dihy15 droxydiphenylmethylene ether and thereafter casting 

the resulting composition. 

10. The method defined in claim 1 wherein the condensation is carried out by mixing the catalyst hardener 

and a foaming composition containing methylol dihy20 droxydiphenylmethylene ether and thereafter projecting the resulting composition on a surface to enable said 

composition to foam thereon. 

is present in the form of technical grade methylol-dihydroxy-diphenylmethylene ether in a mixture containing 

methylol dihydroxy-diphenylmethylene ether together 25 

with water, methylol phenol and dimethylol phenol in 

the presence of a foaming agent, a surface active agent 

and a hardener. 

11. The method defined in claim 1 wherein the condensation is carried out by mixing the catalyst hardener 

and a foaming composition containing methylol dihydroxydiphenylmethylene ether and thereafter injecting 

the resulting composition into a wall space adapted to 

insulate two zones from one another. 

4. The method defined in claim 1 wherein the reaction is carried out with a foaming agent content of 0.1 to 30 

12% by weight and a surface active agent content between 0.01 and 6% by weight. 

S. The method defmed in claim 1 wherein the foaming agent is a saturated aliphatic hydrocarbon, an aliphatic ether or a halogenated hydrocarbon. 35 

6. The method defined in claim 1 wherein the catalyst 

hardener used is selected to bring the pH during the 

reaction to below 4. 

7. The method dermed in claim 6 wherein the catalyst 

hardener is at least organic sulfonic acid comprising at 40 

least one aromatic nucleus, a phenolic hydroxyl group 

45 

50 

55 

60 

65 

12. The method defined in claim 1 wherein the condensation is carried out by mixing the catalyst hardener 

and a foaming composition containing methylol dihydroxydiphenylmethylene ether and thereafter dispersing the resulting composition and permitting particles 

thereof to expand and harden. 

13. The method defined in claim 9, further comprising comminuting the cast product thus produced to 

form insulating granules therefrom. 

14. The product made by the method of claim 1. 

15. Insulation between walls made by the method of 

claim 1. 

• • • • •