CA1113649A - Method for producing phenol foam plastic - Google Patents

Abstract

METHOD FOR PRODUCING PHENOL FOAM PLASTIC
Abstract of the Disclosure A method for producing a phenol foam plastic, consist-ing in that polycondensation of phenols with formaldebyde is conducted with simultaneous foaming and curing in the presence of a foaming agent and an acid or alkaline cata-lyst. Used as the phenols are pyrocatechol, hydroquinone, recorcinol, 5-methyl resorcinol, shale alkyl resorcinols, shale total phenols, or various combinations of said phenols. The method is simple and permits obtaining a foam plastic with improved physico-mechanical properties.

Description

'~itle of tbe Invention ~`IIOD FOR ~RODUCI~G Pl-~NOL FOA~ P~AS'~IC
Field o~ the Invention The present invention relates to methods f'or produc-ing phenol ~'oam plastics. ~he phenol foa~ plastic pro-duced accordin~ ~o the invention can be used as a beat-insulating material in con~truction~ ship building;
machine b~ilding, cb~mical ind~stry~ and refrigeratin~
engineering.
Description of the Prior Ar~
~ nown in the art is a metbod ~or prod~cing a pbenol foam plastic by mising resol pbenol-formaldehyde resin .
wit~ a foaming agent and an acid catal~st. I~ tbis case9 foami~g and curin~ of tbe mi~tl~re take place after a certain period of time (1,5 to 10 minutes).
A serious disadvantage of tbe prior art metbod is , ~
tbe necessity t~ obtain, in advance~ tbe resol phenol-formaldebyde resi~O Tbis resin is produc~d in several stages, namely:
(1) polgcondensation of p~enols witb formaldebyde in tbe presence of a catalys~, at elevated temperatures (j5 to 90C)~ for a long period of time (1~5 to 3 bours);
; (2) cooling and ne~trali~atio~ of tbe resulting product;
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'i (3) separation of tbe resi~ e.g., by vacuum distilla-,~ tionO ' ' '~"

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: , ~ o prod~ce ~sol phenol-foI~aldebyde resin takes mucb time, r1~uires spcci~ll eq~ipment~ cons~Mes ~ucb heat and labor, wbile tbe stora~;e li~2 of resol phenol-formal-. dehyde resin i5 limltod (~p to 2 to 4 month~ and, at bigh tamperat~res, ~p to a rnonth)D
Wben a phenol ~oam plaskic is produced on the basis ~ of said resin7 curing ta]~es a long period of time (1 5 to 10 min~tes) and requires an acid catalyst.
'~he ph~sico-mecbanical properties of tbe p~enol ~oa~ plastic produced by tbe prior art method are not s~fficiently bigb, for example:
apparent density, kg/c~.m 50-100 stress at lO~o linear compression st.rain, kg~/sq cm ., . 0.5-2.0 : . sorptlon moisture co~tent after 24 bours of expos~re to air witb a relative b~midity o~ 98~2~o9 % by mass heat-conductivit~ coefficient at 20~5C, kcal/~sb-C
0-035-0~040 . Summary of tbe Invention It is an object of tbe present inve~tion to provide a simple metbod ~or producing a pbenol ~oa~ plasticD
.~ Another object o~ tbe invention is to provide a method permitting a pbenol ~oam plastlc ~ith improved . pbysico-mecbanical properties to be obtained.
:~ With these and other objects in view, the invention .

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resi~l~s in ~ raet~od for producing a phenol ~oam pl~stic, consi3ting in th~t polycon~ensation OL` phenols with for-maldehyde i5 conductecl siraulta~eously witb ~oaming and curin~ in tbe presence Or a foamin~ a~ent and an acid or alkaline catalys~ the phenols bein~ pyrocat~chol, hydroquinone, resorcinol, 5-metb~l resorcinol~ sbale alkyl resorcinols, shale total resorcinols~ or ~arious combinations of said pbenols~
Owing to:
(1) the use of t~e above pbenols;
(2) tbe introd~ction of a foaming a~ent into tbe starting mixture of monomers; and

(3) the introd~ction o~ an acid or alkaline catalys~
into the starting mi~ture of monomers 9 it bas become possible to conduct t~e processes o~ pol~condensation, foaming and curing in a single stage.
Tbe proposed method fox producin~ a pbenol foam plastic is quite simple. ~he necessity to obtain an intermediate product, i.e., resol phenol-formaldehyde xesin, is ruled o~t3 bence9 no special eguipment is required to produce it. In addition, tbe method can be car~
ried out in a broad temperature range (from 10 ~o 90C) witbin a much sborter period o~ time (~rom 5 to 60 se-conds). ~be above ~actors permit the prod~ctio~ o~ a pbenol ~oam plastic to be substantially inte~si~ied.
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In tbe proposed metbod, the process of curing ca~
be conducted in the presence of botb an acid and , ~ ' ' ' .
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~L3L3~3 - alk~line catalysl; (said catal~1sli serv~s, at tbe same time, as the polycondensation catalyst). In tbe latter c~s~, an acid-Iree phenol ~oam plastic¦is produced, whicb contributes to its low corrosion activit~r ~he phenol foam plastic produced b~ the proposed method ~eatures i~proved physico-~echa~ical cbaracte-ristics, namely:
apparent densit~ kgJc~.m 50-100 stress at 10% li~ear compression strain, k~Jsq.crn ~ 1.0-6~3 heat-cond~ctivity coef~icien~ at 20~5C~ kcalJm-b~C
0~031-0.037 sorption moist~re conte~t after 24 bo~rs of exposure to air witb a relative b~midiky of 98~2%, % by mass 2~ 0-1.0 water absorptio~ duri~g 24 ho~rs, % by vol~me 3L~"O~.l.
It is expedie~t bo ~se, in tbe proposed metbod9 sbale alkyl resorcinols of tbe followi~g composition (% by wei~at):
~ 5-metbyl resorcinol 46-58 .: 2,5-dimetbyl resorcinol 9-12 :` :
5~d~ ~etbyl resorcinol 10-12 5-etbyl resorcinol 10-12 . other alkyl resorci~ols . 13~18, or sbale ~otal resorcinols o~ the following composition (% by weight):

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5-me~hyl :reso:rcinol 25~4-29.4 : ~,5-dimetbyl resorcinol ~0-10.
5-eth~l resorcinol '~5-9.5 2,5-dimetbyl resorcinol 5.4-7.0 monohydric pbenols 1,0-11.4 ` resorcinol 1.6-2.6 ~-methyl resorcinol 1.2~.0 5-n-propyl rssorcinol 1~2-lo~
2-metbyl resorcinol 1.0-104 496-dimeth~l resorcinol . 0~8-1.0 5-n-butyl resorcinol 0.5-0.7 other alk~l resorcino~ 34.0-34.8 . Wi.tb a view to i~tensi~ying the process of foaming and obtaini~g a more structurally bomogeneo~s foam plastic~ the polyco~densation to~etber witb ~oaming and c~ring sbould preferably be conducted in the pre-sence of a non-ionic sur~actant taken in an amount ~- of 1 to 5% of the weight o~ the starting pbenols.
In order to enbance the mechanical strengtb of tbe pbenol foam plastic, the polycondensation togetber witb foaming and c~ri~g sbo~ld ad~isably be co~d~cted in the presence o~ powdered boro~ ~aken.in an a~ount o~
1 to 5~0 of tbe weigbt of ~he starting pbenols.
~o red~ce the sorptio~ mois~ure content a~d mini~ize water absorption of tbe desired foam plasticl tbe poly-condensa~ion together with ~oaming and curing sbould .
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pref`e~ably be conducted in tbe presence o~ polyvinyl alcobol takcn in an amo~nt of 1 to 2~o 4f' the w~ight of the starting phenols~ or in tbe presence o~ poly-ethylene glycol taken in an amo~nt of 0.5 to 2.5~o o~
tbe wai~bt o~ the starting phenols.
Debailed Description of the Inve~tion The proposed method for producin~ a phenoL foa~
plastic is realized as ~ollows:
Phenols (pyrocatechol, hydroquinone, resorcinol, 5-metbyl resorcinol; shale alk~l resorci~ols, shale ~otal pbenols, or various combinations o~ tbese pbenols~
are introduced into a 34-40~0 a~ueous sol~tion o~ formal-debyde. ~be resulti~g ~ixture is thoroughly stirred till complete dissolution Oe the pbenols. Tben, introduced into the solution is a foaming agent and, i~ necessar~, the appropriate addi~ivesg namely: a no~-ionic sureac-tant, powdered boron, poly~inyl alcohol, polyetbylene glycol. Tbe mixture is tboroughly stirred~ and an acid or alkaline catalyst is added tbereto. '~he above compo-nents may be mixed simultaneously, or in any otber se-guence~ in a broad ~emperature range (~rom 10 to 60C)~
A~ber all tbe components ba~e been mixed~ sponta~eo~s beating o~ tbe mixture begins with simultaneous polycon-densation, :eoaming and curing~ wbich processes are over in 5 to 60 seconds.
~ be ~bale al~gl resorcinols and sbale total phenols ; 7 .
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used in the proposcd method are produc~ of` ~rocessing oil shales. The composit:Lon of` tbe sbale alkyl re30I-cinols and sbale total phe~ols ~sed in tbe metbod may vary according to the oil sbale deposits and the tech-nigues of processing shales, which, bowe~er, does not in a~y way af~ect th~ proposed metbod and properties of the end product ~ s the acid catalyst9 ~se may be made, in tbe proposed method, o~, ~or e~ample, mineral and oxganic acids, as well as acid salts.
As tbe alkaline catalyst, use may be made, ~or example, of an alkali metal bydroxide.
As tbe ~oaming agent~ a n~mber o~ compounds can be used9 s~c~ as: carbonates and bicarbonates o~ alkali metals, alkali-eartb me~als and ammoni~m; powders of me-tals standing, in tbe electromotive series, bigher tha~
bydrogen; and liquids boiling or vigoro~sly evaporating at temperat~res below 80C.
As tbe sur~actants, s~ch non-ionic s~r~ace-active agents are ~sed as cellulose esters~ silicone oils, and prod~cts of treatment o~ alkyl pbenols witb etbylene oxide.
For a better ~nderstanding o~ th~ invention, tbe ~ollowin~ examples o~ its practical embodi~ent are give~
by way o~ tration. ~be properties of tbe phanol foam plastic prod~ced according to eacb example are .:

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~13~i~9 listcd in tbe table ~ollowin~ the examples.
$xample 1 100 parts by weight of :resorcinol are mi~ed, at 20C, wi~-h 100 par~s by weigh~ o:~ a 34% aqueous sol~tion of ~ormaldehyde~ 2 parts by weight o~ calci~m carbonate, and 2 parts by weight of polyhydroxy etbylene ester of iso-oc~yl pbenol, of the following formula;
C H - C6H - O(CII2CH20)n l C~2CH2 3 As tbe resulting mixture is bei~g stirred, added thereto are 50 parts bg weight o~ s~lfuric acid baving a speci~ic gravity of 1.12. A~ter said components hava been mixed, tbe processes of polycondensation, foaming and curing are conducted simultaneo~sly to yield a pbe~ol foam plastic.
It takes 15 seconds ~or tbe foam plastic to form.
Example 2 100 parts bg weight of p~rocatecbol are mi~ed~ a~
18C, witb 100 parts by weight of a 34% agueo~s solution of formaldehyde, 1 part by weigbt of the surfacta~t o~ Example 1, and 3 parts by weigbt of powdered al~
n~m. Added to tbe resulting mixture~ witb stirring, are 80 parts by weigbt o~ sulf~ric acid ha~ing a speci-~ic gravity of 1.49. hfter said components bave been mixed, tbe processes of polycondensation, foaming and c~ring are conducted simul~aneo~sly to yield a pbenol foam plastic~
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Example 3 , .~ , .
~ 100 parts by weight of 5-metbyl resoxcinol are mi~e~,,,, ~
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at 15 C, with 100 parts b9 ~eight of a 34% aq~eo~s sol~-tion of formalde~yda and 20 parts b~ wei~bt o~ a lig~id foaming agerlt~ name:L~ isopentane~ ~d~ed to ~be res~lting mix~ro, witb stirring, are 50 parts by weigbt of s~lfuric acid baving a specific gravit~ of` 1.52.
As a result, a phenol foam plastic is obtained Example 4 100 parts by weigbt o~ hydroguinone axe mixed, at 60C, wi~b 100 parts by weigbt o~ a 34% aqueous solu-tion of ~ormaldehyde and 3 parts by weigbt o~ calci~m bicarbonate. Added to the resulting mixture, witb stir-ring; are 80 part~ by weig~t o~ s~l~uric acid having a speci~ic gravity o~ 1.52. 5 seconds a~ter bbe components have be~n mixed, ~oxmation of a pbe~ol ~oam plastic is completed.
EXample 5 s 100 parts by waigbt of resorcinol.are mixed; at 20C, with 120 parts b~ wei~bt o~ a 34~ aqueous solution o~
~ormaldebyde, 3 parts b~ weigbt of polybydroxy etbylene ester of isooctyl pbenol, of tbe following ~ormula:
C E~ - C6H4 - 0(CH2CH2)n.l ~ CH2CH2H' and 3 parts by weigbt of ammoni~m carbonate. Added to . tbe res~lting mixt~re, witb stirring~ are 83 parts by ~:~ weigbt of a 20% a~ueo~s solution o~ sodi~m bydroxide.
As a res~l~ o~ simultaneous pol~conde~sation, foaming : and curi~V a phenol ~oam plastic is produced, wbose ~: ~ormation i.s completed a~ter 30 seco~dsO

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'" '- ' ~3 ~ 9 ~xample G
100 par~ by weig~t ot 5-me~hyl xesorcinol are mi~od with 90 pclrt~ by weight of a 40% aqueows solution of ~ormaldehyde, 3 parts by we:Lgbt of powdered alumin~m~
and 3 parts by weigbt ot` the sur~actant of Example 1.
Added to th~ res~lting mi~tllre, witb stirri~3 are ~0 parts by weight of a 20% aqueous solution of potas-sium bydroxide After intensive stirrin~ o~ ~he compo-~ents, tbe process of for~atiion o~ a pbe~ol foam plastic is completed. It takes 60 seco~ds ~or the ~oam plastic to form.
Example 7 100 parts by weigbt of sbale alkyl resorcinols (composition, in % by weigbt: 5-metbyl resorci~ol - 46;
: 2,5-dimet~yl resorcinol - 12~ 4,5-dimethyl resorcinol -12; 5-etbyl resorcinol - 12; otber alkyl re~orci~ols are mix~d~ at 30C, witb 100 parts by wel~bt o~ a 34Y0 ; aq~eo~s solution o~ ~ormaldebyde and 3 parts b~ weigh~
o~ calcium carbonate. Added to tbe resulting mixture, witb s~irring, are ~5 parts by weight o~ sul~uric acid bavi~g a specific gravi~y o~ 1.09. A~ter intensive .; stirri~ of tbe components, the process o~ formabion .. - o~ a phe~ol foa~ plastic is over. It takes 15 seconds . ~or tbe foam plastic to form.
Example 8 100 parts by weigbt o~ ~bale aIk~l resorci~o~s ': ' : ~ . .. ~. . -`~: . " ' , ' . ' ~ ' ', , .

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(composi~ion, in % by wei~ht: 5-methyl resorcinol - 5~;
2,5-~ime~yl r~sorcinol - 9; 4,5-dimet~yl resorcinol 10;
5-ethyl resorcinol - 10; otber alkyl resorcinols - 13) are Inixed, a~ 20C, with 100 parts b~ weigbt of a 34~o aqweous solution oY formaldebyde~ 2 parts by weigbt o~
powdered aluminum~ and 5 parts by weight of tba sur~ac-s tant of Example 1. Added to the resul~ing mixtur~, witb stirring, are 45 parts by weight of phosphoxic acid t bavin~ a speci~ic gravity o:E 1.08. As a result of mixin~, a pbenol ~oam plastic i5 obtained. It takes 40 seconds for tbe foam plas~ic to ~orm.
Example 9 100 parts bg weight of shale alkyl resorcinols (compo-,.
sitionj in % by weigbt: 5-methyl resorcinol - 50;
2,5-dimetbyl re40rcinol - 10.5; 495-dimetbyl resorcinol -;- .
12; 5-etbyl resorcinol - 10.5; otber alkyl resorcinols -17) are mixed, at 20C, with 130 parts by weight of a 3~% aq~eo~s sol~tio~ oY formaldebyde and 10 parts by weigbt of a liquid ~oaming agent, namely, difluorodicblo-romethane. Added to tbe resulting mi~t~re~ witb stirring, are 50 parts by weigbt of byd~ochloric acid baving a speci~ic gravity of 1.09. As a result of sim~ltaneo~s polycondensation, foa~ing and c~ring~ a pbenol ~oam plastic is obtained.
Example 10 100 parts by weight of s~ale alkyl resoroinols (com-.
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~ 3~ ~9 position, in % by weigbt: 5-m~tbyl r~sorcinol - 52;
2,5-dime~byl resorcinol - 10.5; 475-di~etbyl resorcinol -11; 5-ethyl resorcinol 11; other alkyl resorcinols 15.5) are f~ixed, at 25C, witb ~0 parts by weigbt of a 40~o agueous solution of' formaldebyde, 3 parts by weiæbt of powdered alumi~um, and 3 parts by weigbt of the ~r-factant o~ Exa~ple 5. ~d~ed to ~he resulting mixt~re, witb s~irring, are ~5 parts by weight of a 20% aq~eous sol~tion of sodium bydroxide. ~s a result o~ simultaneo~s polycondensation~ foa~ing and curin~9 a pbenol foa~
plastic is obtained. It takes ~5 seconds for tbe foa~
plastic to for~.
:E~ample 11 100 parts by weigbt o~ s~ale total pbe~ols (co~posi-tionjin % by weight: 5-metbyl resorcinol - 25~4;

4,5-dimatbyl resorcinol - 10.8; 5-etbyl resorcinol - 9.5;
2,5-dimet~yl resorcinol - 7.0; monoh~dric pne~ols - 3.0;
resoxcinoL - 2.6; 4-~ethyl resorcinol - 2~0; 5-n-propyl ; ~
; resorcinol - 108; 2-metbyl resorcinol - 1.4; 4,6-dimetbyl resorcinol - 1.0; 5-n-butyl resorcinol - 0.7; other alkyl resorcinols 3~.8) are mixed, at 10C, witb 80 parts by ~eigbt of a 34Y0 aqueo~s sol~tion of for~alde--~ byde, 5 parts by weigbt of calciu~ carbonate 3 an~ 5 part3 by weight of tbe surfactant of Example 1. ~dded to tbe resulting mixture, with stirri~gt are 40 parts by weigbt ~ -~: of sul~uric acid baving a specific gravity of 1.18.

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A~7 a result o~7 simLIlt,anco~s polycon/le~6~tion, ~70~ming and curing7 ~ pt~enol ~70am plastic is prod~ced. Ik ta~es 15 seconds for tbe t70am plastic to form.
Example 12 100 parts by weight of 7hale total phenols (composi-tion, in ~0 by ~vei~rbt: 5~metbyl resorcinol 29.4;
4,5-dlmethyl resorcinol - 8,0; 5-etbyl resorci~ol - 7.5;
2,5-dimetbyl resorci~ol - 5.4; monohySlric phenol~ - 9.4;
resorcinol - 1.6; ~-metbyl resorcinol _ 1.2; 5-n-propyl resorcinol - 1.2; 2-metbyl resor¢inol l.Oi 4,6-dimetbyl resorcinol - 0.8; 5-n-butyl resorcinol - 0~5;
otber alkyl resorcinol~ - 34.0) are mixedg at 20C, witb 60 parts by weigbt of7 a 40Y0 agueous solutio~ of formaldebyde and 3 parts by weigbt o~7 powder~d aluminum.
Added to tbe resulting mix~ure, witb stirring, are 50 parts by weigbt of pbosphoric acid having a specific gravity of 1.19. As a res~lt of sim~lta~eo~s polgconde~-sa~ion, foaming and curing, a pbenol foam plastic is obt a ined O
Example 13 100 parts by weigbt o~ sbale total phe~ols (composi-tion, in ~0 by weigbt: 5-me~byl resorcinol - 27.4;
435-dimetbyl resorcinol - 9~4; 5-etbyl resorci~ol - 8.59 2,5-dimetbyl resorci~ol - 6.2; mo~obydric pbenol~ - 6.2;
resorcinol - 2.1; 4-metbyl resorcinol - 1.6; 5-n-p~opyl resorcinol - 1.5; 2-metbyl resorcinol - 1.2;

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~,6 dirnethyl r~sorcinol - 0 9; 5~-butyl resorcinol - 0~6;
othar alkyl resorcinols _ 34.4) aro mixed, at 20C7 with 100 parts by ~veigh~ of a 37% agueous solution of formal-deb~de and 4 parts by weigbt of ammoni~m carbonate.
Added to the resulting mixbllre, witb stixring, are 20 parts by weight o~ a 20~o agueo~s solution o~ sodium hydroxide A~ter mixin~ all o~ the above components, tbe processes of polycondensation, ~oaming and c~ri~g are conducted simultaneously to yield a phenol foam plastic.
Example 14 100 parts by weigbt o~ sbale total pbenols (composi-tion, in % by weight: 5-methyl resorcinol - 29.0;
4,5-dimebbyl resorcinol - 10~8; 5-ethyl resorcinol - 9.5;
2,5-dimetbyl resorcinol - 6.~, monobydric phenols - 1.0;
resorcinol - 2.3i 4~m0th~1 resorci~ol _ 1.7; 5-n-propyl resorcinol - 1~6i 2-metbyl resorcinol - 1.3; 4,6-dime~thyl resorcinol - 1.0; 5-~-butyl resorci~ol - 007; obher alkyl resorcinols - 34.3) arc mixed, at 20C, witb 120 parts by weigbt of a 34% agueous solution of ~ormaldehyde, 1.5 parts by woight of calcium carbona~e, 3 parts by weight o~ t~e s~rfactant of Exa~ple 5~ and 1 part by weigbt o~ powdered boron. Added to tbe resulting mixture, witb st1rring, are 20 parts by weigbt o~ sulf~ric acid baving a specific gravity of 1,12. ~fter ~ixi~g all o~ tbe above components, the processes of pol~condensation9 foaming and curi~g aro conducted simultaneously to gield a pbenol ~oa~
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~ample 15 100 par~s by weight of shale ~otal pbenols ol~ the compo~ition of ~xample 12 are mixed, at 20C~ with 80 parts by weight of a 34~, aqueous solu~ion of formal-dehyde, 2 parts by weight c,~ calcium carbonate, a~d

5 parts by weight of powdered boron. Added to tbe re-- sulting ~ixture, with stirring, are 20 parts by weight of s~lf~ric acid ha~in~ a speci~ic gra~itg o~ 1~12.
After mixing all o~ tbe above compone~ts, the processes o~ polycondensation~ foaming and curing are conducted simulta~eously to yield a pbenol foam plastic.
Example 16 100 parts by ~ei~ht of sbale total phe~ols of tbe compo~itionbf Example 11 are mixed witb 100 parts by weigbt o~ a 34% aqueous solutio~ of ~ormaldehyde, 2 parts by ~/eigbt of calci~m carbonate~ 2 parts by weigbt of the sur~actant of hxample 5, and 2,~ parts by weig~t o~ powdered boron~ Added to tbe resultin~
mixture, witb stirri~g, are 20 parts bg weighb of s~l-furic acid baving a ~pecific gravity of 1.12 Aa a resulb, a pbenol foam plastic is obtained.
Example 17 100 parts by weight o~ sbale total phenols o~ tbe compo ition of Example 12 are mixed with 70 parts by weight o~ a 40Yo agueous sol~tion of formaldebyde, 3 parts by weigbt of calcium carbonateJ a~d 1 part by weigbt o~
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polyvinyl alcobol, Added to tbe rcs~lting mixtur-~) rJith s~ixring, arq 30 part~ by wcigbt o~ sulfuric acid havin~
a specific gravi~y o~ 1.12. ~s a result, a phenol ~oa~
plastic i5 obtainod~
E~a~ple 18 100 parts by ~eight o~ sbale total phenolq o~ tbe composition of Example 13 ar~ mixed with 200 parts bg weight of a 40% agueous so~ution o~ ~oxmaldeb~de, 4 parts by weight of calcillm carbonat~/ 3 parts by weigbt of the surfactant o~ Example 1, a~d 2 parts by weight of polyvinyl alcohol. Added to tbe r~s~lting mixt~re~ witb stirring, are 40 parts by ~eight of sul-furic acid bavi~g a speci~ic gra~ity of 1~120 A~ter mixlng all of tbe above components, tbe processes of polycondensatio~, foami~g and curing are conductod simulta~eously to yield a pbe~ol ~oam plastic.
Example 19 100 parts by weigbt of sbale total phenols of tbe composition o~ Example 13 are mixed with 100 parts by weigbt of a 3~% aq~eo~s solu~io~ of ~ormaldebyde, 3 parts bg weight o~ calcium carbonate, 3 parts by weigbb of the sur~acta~t o~ Example 5, and 0~5 parbs b~ weigbt of polyetbylene glycol. Added to tbe resulting mixture~
with s~irri~, are 30 parts by weight o~ s~lfuric acid having a ~pecific gravity of 1.120 ~B a res~lt, a phe~ol ~oam plas~ic is obtained.
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EX~mple 20 100 parts by weigbt of sbale ~otal phenols of tbe co0-position o~ ~xa~le 11 are mixed witb 150 parts by weigh~
of a 40% aqueous solutio~ o~` ~orm~ldeb~de, 4 parts by weigbt o~ calcium carbonate 7 and 2.7 par~s by wei~bt of polyetbyl~ne glycol~ Added to tbe re~lti~g mixt~re, with stirring, are 40 parts by weigbb of sulf~ric acid ba~ing a speci~ic gra~i-ty of 1.12~ As a result~ a pbenol ~oam pla~tic i9 obtained.
Example 21 100 par~s by weigbt o~ sbale total pbenols of tbe com-position of Example 12 are mixed with ~0 parts by weigbb of a 37% agueous solution of formaldebyde, 3 parts by weigbt o~ calcium carbonate, 3 parts by weigbt o~ the sur~ac~ant of Example 1, and 1.5 parts by weight of polyetbylene glycol~ Added to the resulting mixture~
with stirring, are 30 parts by weigbt o~ sul~uric acid baving a specific gravity o~ 1.12~ A~ter mixing all o~
tbe above components, tbe processes o~ polycDndensation~
foa~ing and curing are conducbed simultaneously to gield a pbenol ~oa~ plastic.
Example 22 50 part~ by weight of resorcinol and 50 parts by weigbt o~ 5-metbyl resorcinol are ~ixed witb 100 parts by weigbt o~ a 37% aqueous ~olution of ~or~aldebyde and 3 parbs by weighb o~ calciu~ car~ona~e~ A~ded to tbe resulting mix-:
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Example 23 ~ 30 parts by weight of pyroeateebol, 30 parts by weight of bydroguinone and 40 parts by weight of 5-methyl re-soreinol are mixed witb 1~0 parts by weight o~ a 40%
ag~eou~ solution of formaldebyde, 2 parts by weigbt of tbe sur~aetant of Examplo 1~ 3 parts by weight o~ cal-eium earbonate, a parts by wei~hb of.powdered boron, and 1 part bg weight of polyvinyl alcobolO Added to tbe ~ . res~ltin~ mixt~re~ witb stirring, are 40 parts by weigbb .~ of sulfuric aeid baving a speci~ic gravitg o~ 1012.
After mixing all of tbe abo~e components, tbe proeesses o~
;~ polyeondensa~ion, ~oaming and euring are eondueted simultaneouslg ~o yield a pbenol ~oa~ pla~ti¢0 Exampl~ 24 : . For eo~parison, this example illuitra~es bow p~enol - ~oam plastie i~ obtained by the prior art met~od~
First~ ~ liguid resol. pbenol-~ormaldehyde resin is obtained by way o~ polyeondensation of pbenol ~94 parts ., -; , , .: by weigbt) witb ~ormaldeh~de (130 parts by weigbt o~ a 37% agueou~ solution) in tbe presenee of 1.5 parts by ~ ~ weigbt of ~lodi~ b~droxideO ~he polyeonden~ation i8 :. eondueted at 75 ~o 80C ~or 2.5 to 3.hours.

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Tbe rosulting product ls neutralized with bo.ric acid to pH - 7.0-7.3 and conce~brated by distilling off wa~er and vola~ile compounds under vacuum (ultimate pressure of 100 to 160 mm Hg) ~o a spoci~ic gravity of : 1.24 g/cu.cm, ab 20C.
~ ~ Tbe obtained resol pb~nol-formaldebyde resin is raixed witb 1.4 parts b~ weight of powdered al~min~m, 4 parbs by weight 4f ths surfactant o~ Example 1, a~d added to tho mixture are 17 parts by weight o~ bhe produ~ o~
polyconden~ation of sulfopbenol urea with formaldebyde and 42 parts by wei~ht o~ orthophospboric acid. 1.5 to 2 ~in~.tes after bbe components bave been mixed, foaming and curing of bbe mixture start. As a result, a pbenol foam plastiG ia obtained.
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Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method for producing a phenol foam plastic, con-sisting in that polycondensation of phenols with formal-dehyde is conducted with simultaneous foaming and curing in the presence of a foaming agent and an acid or alkaline catalyst, the phenols being pyrocatechol, hydroquinone, resorcinol, 5-methyl resorcinol, shale alkyl resorcinols, shale total phenols, or various combinations of said phenols.

2. A method as claimed in claim 1, wherein shale alkyl resorcinols of the following composition (% by weight) are used:
5-methyl resorcinol 46-58 2,5-dimethyl resorcinol 9-12 4,5-dimethyl resorcinol 10-12 5-ethyl resorcinol 10-12 other alkyl resorcinols 13-18.

3. A method as claimed in claim 1, wherein shale total phenols of the following composition (% by weight) are used:
5-methyl resorcinol 25.4-29.4 4,5-dime thyl resorcinol 8.0-10.8 5-ethyl resorcinol 7.5-9.5 2,5-dimethyl resorcinol 5.4-7.0 monohydric phenols 1.0-11.4 resorcinol 1.6-2.6 4-methyl resorcinol 1.2-2.0 5-n-propyl resorcinol 1.2-1.8 2 methyl resorcinol 1.0-1.4 4,6-dimethyl resorcinol 0.8-1.0 5-n-butyl resorcinol 0.5-0.7 other alkyl resorcinols 34.0-34.8

4. A method as claimed in claims 1 to 3, wherein the polycondensation together with foaming and curing are conducted in the presence of a non-ionic surfactant taken in an amount of 1 to 5% of the weight of the starting phenols.

5. A method as claimed in claims 1 to 3, wherein the polycondensation together with foaming and curing are conducted in the presence of powdered boron taken in an amount of 1 to 5% of the weight of the starting phenols.

6. A method as claimed in claims 1 to 3, wherein the polycondensation together with foaming and curing are conducted in the presence of polyvinyl alcohol taken in an amount of 1 to 2% of the weight of the starting phenols.

7. A method as claimed in claims 1 to 3, wherein the polycondensation together with foaming and curing are conducted in the presence of polyethylene glycol taken in an amount of 0.5 to 2.5 of the weight of the starting phenols.

8. A phenol foam plastic produced by the method claimed in claims 1 to 3.