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Claims  |
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I claim:
1. A process for producing polyisocyanate organic silicate cellular solid
products by the following steps:
(a) mixing component (B), an organic polyisocyanate or polyisothiocyanate,
with component (A), an oxidated silicon;
(b) agitating the mixture at 20.degree. to 60.degree. C. for 10 to 30
minutes thereby producing a polyisocyanate silicate prepolymer;
(c) admixing component (C), an organic additive, and component (D), a
curing agent with the polisocyanate silicate prepolymer, and allowing the
resultant mixture to react, wherein said organic additive contains from 1
to 9 carbon atoms, has a molecular weight of from 32 to 400 and is
selected from the group consisting of monoalcohols, monothioalcohols,
monophenols, monothiophenols, halomethyl group containing compounds,
nitriles, esters, ethers, thioethers, ketones, nitro-group containing
compounds, monocarboxylic acid chlorides, monocarboxylic acid bromides,
monosulphonic acids or salts thereof, monocarboxylic acids or salts
thereof, and aldehydes, with the proviso that when said organic additive
is a monoalcohol, monothioalcohol, monophenol, monothiophenol or
monocarboxylic acid, said mixing of (C) and (D) into (A and B) takes place
substantially simultaneously.
2. The process of claim 1 wherein the oxidated silicon compound is selected
from the group consisting of silicoformic acid, natural occurring oxidated
silicon compounds with free silicic acid groups and silica sol.
3. The process of claim 1 wherein said organic additive is selected from
the group consisting of monoalcohols, monocarboxylic acids or salts
thereof and monosulphonic acids or salts thereof.
4. The process of claim 1 wherein the curing agent is selected from the
group consisting of water, water containing 10% to 70% by weight of an
alkali metal silicate, water containing 20% to 70% by weight silica sol,
water containing 5% to 40% by weight of magnesium oxide in the form of a
colloidal dispersion, alkali metal metasilicate pentahydrate selected from
the group consisting of sodium metasilicate pentahydrate, potassium
metasilicate pentahydrate, lithium metasilicate pentahydrate, and mixtures
thereof.
5. The process of claim 1 wherein component (C) is a compound or radical
containing a functional group corresponding to one of the following
general formulae: ROH, RSH, RCH.sub.2 Cl, RCH.sub.2 I, RCN, RNO.sub.2,
RCOCl, RCOBr, RSO.sub.2 Cl, RCOOH, RSO.sub.3 H, RCOO.sup.-,
RSO.sub.3.sup.-, ROR, RCOOR or
##STR2##
wherein R is CH.sub.3 --, C.sub.2 H.sub.5 -- or C.sub.3 H.sub.7 --.
6. The process of claim 1, wherein said organic additive is selected from
the group consisting of methanol, ethanol, propanol, isopropanol, butanol,
isobutanol, t-butyl alcohol and the isomeric pentanols, hexanols and
heptanols, cyclohexanol, methylcyclohexanol, methallyl alcohol, allyl
alcohol, cyclohexano-methanol, benzyl alcohol, butylmercaptan, phenols,
thiophenol and thiocresols; formaldehyde, acetaldehyde, propionaldehyde,
butyl aldehyde, pentanals, hexanals, heptanals, octanals and the
corresponding semi-acetals and full acetals; formic acid, acetic acid,
propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexane
carboxylic acid, heptane carboxylic acid, cyclohexane carboxylic acid,
benzoic acid, toluic acid; acetyl chloride, propionic acid chloride,
acetyl bromide, acid chloride of C.sub.4 -C.sub.6 monocarboxylic acids,
methane sulphonic acid chloride, benzenesulphonic acid chloride, p-toluene
sulphochloride, o-toluene sulphochloride, carbamic acid chlorides,
phenylcarbamic chloride; methyl acetate, ethyl acetate, propyl acetate,
butyl acetate, amyl acetate, the methyl and ethyl esters of propionic,
butyric, pentanoic, hexanoic, and heptanoic and the corresponding isomeric
compounds; methyl ethyl ether, cyclohexyl methyl ether, methyl butyl
ether, phenol methyl ether, thiophenol methyl ether, cresol methyl ether,
tetrahydrofuranomethyl-methyl ether; ethyl chloride, ethyl bromide, ethyl
iodide, n-propyl chloride, n-propyl bromide, n-propyl iodide, isopropyl
chloride, isopropyl bromide, isopropyl iodide, butyl chloride, butyl
bromide, butyl iodide, benzyl halides, hexahydrobenzyl halides,
cyclohexanomethyl chloride, epichlorohydrin,
2-ethyl-2-chloromethyl-oxetane, and 2-ethyl-2-chloromethyloxetane; methyl
ether ketone, methyl-isopropyl ketone, methyl-isobutyl ketone,
methyl-isoamyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone,
methyl-t-butyl ketone, methyl-furanyl ketone, methyl-tetrahydrofuranyl
ketone, methyl-heptyl ketone, ethylhexyl ketone, acetophonone,
.omega.-chloroacetophenone and propiophenone; acetonitrile, propionitrile,
butyronitrile, tolunitrile, hexahydrobenzonitrile, acrylonitrile,
allylnitrile, methallylnitrile and methacrylonitrile; nitromethane,
nitroethane, nitrohexane, nitrobenzene, chlorinated nitrobenzynes,
nitrocyclohexanes, brominated nitrobenzenes, benzyl nitrate and
nitrotoluene; methanesulphonic acid, ethanesulphonic acid, butanesulphonic
acid, benzenesulphonic acid, 2-toluenesulphonic acid, 4-toluenesulphonic
acid, chlorsulphonic acid esters and sulphonic acid esters;
trimethylphosphite, trimethylphosphate, triethylphosphite and
triethylphosphate; calcium lignosulfonate, lignosulfonic acid sodium
salts, and lignin sulfate produced by alkali process and mixtures thereof.
7. The process of claim 1 wherein methanol is the organic additive of
component (C).
8. The process of claim 1 wherein the proportion by weight of component
(B), (polyisocyanate), to component (D), (curing agent) is from 70:1 to
20:80.
9. The process of claim 1 wherein the proportion by mols of component (B),
(polyisocyanate), to component (A), (oxidated silicon compound) is fron
2:1 to 1:2.
10. The process of claim 1 wherein component (C) (organic additive), is
used in a quantity of from 1% to 30% by weight, based on component (B),
(polyisocyanate).
11. The process of claim 1 wherein up to 50% by weight, based on the
reaction mixture, of a chemically inert blowing agent boiling within the
range of from -25.degree. to 80.degree. C. is added.
12. The process of claim 11 wherein the reaction is accompanied by foaming.
13. The process of claim 1 wherein the mixture contains from 0.001 to 10%
by weight, based on the reaction mixture, of an activator selected from
the group consisting of tertiary amines, organo-tin compounds and
silaamines.
14. The process of claim 1, wherein the mixture contains up to 20% by
weight, based on the reaction mixture, of a foam stabilizer.
15. The process of claim 1 wherein the mixture contains up to 20% by
weight, based on the reaction mixture, of an emulsifying agent.
16. The process of claim 1 wherein inorganic or organic particulate or
pulverulent materials are added to the reaction mixture.
17. The product of the process of claim 1.
18. The process of claim 1 wherein the oxidated silicon compound of
component (A) is reacted chemically with a polyol, selected from the group
consisting of glycerol, ethylene glycol, propylene glycol, butylene
glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol,
hexamethylene glycol, diethylene glycol, dipropylene glycol, polypropylene
glycol, tetraethylene glycol, ether glycols, Bisphenol A, resorcinol, bis
(beta-hydroxyethyl) terephthalate,
2-ethyl-2-(hydroxymethyl)-1,3-propanediol, pentaerythritol, quinitol,
mannitol, sorbitol, methylglucoside, glucose, starches, fructose, cane
sugar, dextrines, dibutylene glycol, polybutylene glycol, polyester resins
with free hydroxyl groups, polybutadienes which contain free hydroxyl
groups, polycarbonates which contain free hydroxyl groups, trimethylol
ethane, trimethylol propane, hexane-1,2,6-triol, polyestor silicates
containing free hydroxyl groups, butane-1,2,4-triol, 1,8-octanediol and
mixtures thereof, to produce a polyol silicate and in the amount of 1 mol
of oxidated silicon compound to 0.5 to 2 mols of the polyol and then
reacted with the polyisocyanate in step (a) of claim 1 as component A.
19. The process of claim 1, wherein an alkali catalyst, selected from the
group consisting of sodium hydroxide, sodium carbonate, potassium
hydroxide, potassium carbonate, sodium silicate and other alkali metal
salts of weak acids, and added in the amount of 1% to 10% by weight, based
on the oxidated silicon compound, in step (a) of claim 1.
20. The product of the process of claim 18.
21. The process of claim 1 wherein up to 93% by weight, based on weight of
the mixture, of a water-binding component is added and wherein the
water-binding component is a hydraulic cement, synthetic anhydrite, gypsum
or burnt lime.
22. The product of the process of claim 21.
23. The process of claim 1 wherein a dry granular alkali metal silicate,
selected from the group consisting of sodium metasilicate pentahydrate and
potassium metasilicate pentahydrate in the amount of up to 50% by weight,
based on the weight of the oxidated silicon compound (component A) is
added with the oxidated silicon compound in step (a) of claim 1.
24. The process of claim 1 wherein an additional step is taken wherein the
polyisocyanate (component B) is treated with sulfur trioxide thereby
producing a polyisocyanate which contains sulphonic acid and/or suphonate
groups.
25. The product of the process of claim 24.
26. A polyisocyanate organic silicate plastic, having high strength,
elasticity, dimensional stability with increase in temperature and flame
resistance, is prepared by the process which comprises substantially
simultaneously mixing and reacting an organic polyisocyanate or
polyisothiocyanate, an hydrated silica an organic additive selected from
the group consisting of monoalcohols, monothioalcohols, monophenols, and
monothiophenols, said organic additive having a molecular weight of up to
about 400, and a curing agent selected from the group consisting of water,
water containing polyols, and water containing an alkali metal silicate,
said polyisocyanate organic silicate plastic being the solid/cellular
solid product.
27. The process of claim 1 wherein the components (A), (B), (C) and (D) are
substantially simultaneously mixed.
28. The product of the process of claim 27.
29. The process of claim 1 wherein the polyisocyanate (component B) is
selected from the group consisting of 2,4-toluene diisocyanate,
2,6-toluene diisocyanate or mixtures thereof.
30. The process of claim 1 wherein an additional step is taken wherein the
organic polyisocyanate is reacted with a polyol to produce a liquid
isocyanate-terminated polyurethane prepolymer and used as component (B);
the polyol is added in the ratio of 1 to 50 mols to 5 to 99 mols of the
polyisocyanate.
31. The process of claim 1 wherein a polyol is added to component (D) in
the ratio of 1 to 50 mols to 50 to 99 mols of component (B).
32. The process of claim 1 wherein an additional step is taken wherein 10%
to 50% by weight of a dry granular alkali metal silicate, selected from
the group consisting of potassium metasilicate pentahydrate, and
commercial sodium silicate, percentage based on weight of Component A, and
is added in step (a) of claim 1. |
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Claims |
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Description |
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BACKGROUND OF THE INVENTION
This invention relates to a process for the production of polyisocyanate
silicate prepolymers and polyisocyanate organic silicate solid/cellular
solid products. The polyisocyanate silicate prepolymer will react
chemically with many organic compounds and polymers, inorganic compounds,
organic silicate compounds and polymers, and mixtures thereof to produce
useful polyisocyanate organic silicate solid/cellular solid products.
The products produced by this invention may be utilized as thermal
insulating material, noise insulating material, floatation materials in
boats, shock-resistant packaging, cushions, as fiber, as coating agents,
as fillers, as impregnating agents, as adhesives, as casting material, as
putty material, as constructional components of a building, etc. The
products have improved heat and flame resistant properties. The products
are novel and economical; some have wood-like physical properties. The
products may be sprayed or mixed in place.
In the process according to the invention at least 4 components are used to
produce the novel polyisocyanate organic silicate solid/cellular solid
products as follows:
1. Component A: an oxidated silicon compound
2. Component B: an organic polyisocyanate or polyisothiocyanate
3. Component C: an organic amphiphilous compound
4. Compound D: a curing agent and/or activator
Component A
The oxidated silicon compounds may be produced by any of the commonly known
methods in the arts. They are preferred to be in a fine granular form. The
oxidated silicon compounds include hydrated silica, hydrated silica
containing Si-H bonds (silicoformic acid), silica and natural occurring
oxidated silicon compounds with free silicic acid groups. The hydrated
silica includes various silicon acids such as dry silicic acid gel,
orthosilicic acid, metasilicic acid, monosilandiol, polysilicoformic acid,
orthosilicoformic acid (Leucone), silicoformic acid and silica sol.
Hydraulic cements such as Portland cement, quick-setting cement, mortar
cement, blast-furnace Portland cement, sulphate-resistant cement, brick
cement, mild-burnt cement, natural cement, lime cement, gypsum cement,
calcium sulfate cement, pozzolan cement, etc., contain oxidated silicon
compounds and may be used in this invention. Hydrated silicate is the
preferred oxidated silicon compound.
There are many different kinds of cement which may be used; in general, any
mixture of fine ground lime, alumina and silica that will set to a hard
product by admixture of water which combines chemically with the other
ingredients to form a hydrate may be used. Detailed descriptions of the
many kinds of cement which react with sand and rocks to produce concrete
may be found in "Encyclopedia of Chemical Technology", Volume 4, Second
Edition, Published by Kirk-Othmer, pages 684-710, as well as in other well
known references in this field.
Component B
The polyisocyanate organic silicate solid/cellular solid products may be
modified or improved by adding organic compounds, inorganic compounds,
and/or organic-silicate compounds and polymers. These compounds may be
added before the isocyanate, and the oxidated silicon compounds are
reacted together, or they may be added after the polyisocyanate silicate
prepolymer is produced. Organic polyols, polyesters, polyether glycols,
organic polyol silicates, polyester silicates and polysulfides,
polybutadiene, butadiene-styrene copolymers and butadiene-acrylonitrile
copolymers which contain free hydroxyl groups may be used in this
invention. These hydroxyl containing compounds, (polyols), polymers and
copolymers may be first reacted with a polyisocyanate to produce a liquid
isocyanate-terminated polyurethane prepolymer, and this may be used in
this invention. The polyols may be reacted chemically with oxidated
silicon compounds to produce organic hydroxy silicate compounds and their
condensation products and may be used in this process. The method to
produce the organic hydroxy silicate compounds and condensation products
(polyester silicate polymers) may be found in U.S. Pat. Application No.
765,050, filed on Feb. 2, 1977, by David H. Blount. The oxidated silicon
compounds may be first reacted with a polycarboxylic acid and/or a
polycarboxylic acid anhydride to produce a silicic acid organic acid
anhydride which may then be reacted with a polyol to produce a polyester
silicate polymer which may be used in this invention.
Any suitable polyisocyanate or polyisothiocyanate may be used in this
invention. For example, arylene polyisocyanates, such as tolylene,
metaphenylene, 4-chlorophenylene-1, 3-, methylene-bis (phenylene-4-),
biphenylene-4, 4'-, 3,3'-dimethoxybiphenylene-4,4'-;
3,3'-diphenylbiphenylene-4,4'-, naphthalene-1,5-, and
tertrahydro-naphthalene-1,5-diisocyanates and triphenylmethane
triisocyanate, alkylene polyisocyanates such as ethylene, ethylidine,
propylene-1,2-, butylene-1,4-, butylene-1,3-, hexylene-1,6-,
decamethylene-1,10-, cyclohexylene-1,2-, cyclohexylene-1,4-, and
methylene-bis (cyclohexyl-4,4-) diisocyanates. Phosgenation products of
aniline-formaldehyde condensation may be used such as
polyphenyl-polymethylene, polyisocyanates. Polyisothiocyanates, inorganic
polyisothiocyanates, polyisocyanates which contain carbodiimide groups as
described in German Pat. No. 1,092,007 and polyisocyanates which contain
urethane groups, allophanate groups, isocyanurate groups, urea groups,
imide groups or biuret groups may be used to produce polyisocyanate
silicate prepolymers or polyisocyanate organic silicate solid/cellular
solid products. Mixtures of the above mentioned polyisocyanates may be
used.
It is generally preferred to use commercial, readily available
polyisocyanates such as toluene-2,4- and -2,6 diisocyanate and any mixture
of these isomers, ("TDI"), ("crude MDI"),
polyphenyl-polymethylene-isocyanates obtained by aniline-formaldehyde
condensation followed by phosgenation, and modified polyisocyanates which
contain carbondiimide groups, urethane groups, allophanate groups,
isocyanurate groups, urea groups, imide groups or biuret groups,
("modified polyisocyanates").
Other polyisocyanates may be used in this invention such as polyisocyanates
which contain ester groups such as listed in British Pat. Nos. 956,474 and
1,086,404 and in U.S. Pat. Nos. 3,281,378 and 3,567,763, polyisocyanate
reaction products with acetals according to German Pat. No. 1,072,385
Polyisocyanates prepared by telomerization reactions as described in
Belgian Pat. No. 723,640, polyphenyl-polymethylene polyisocyanates as
described in British Pat. Nos. 874,430 and 848,671 polyisocyanates which
contain carbodiimide groups as described in German Pat. No. 1,092,007,
perchlorinated arylpolyisocyanates such as those described e.g. in German
Pat. No. 1,157,601, polyisocyanates which contain allophanate groups as
described e.g. in British Pat. No. 994,890 and in Belgian Pat. No.
761,628, and the diisocyanates described in U.S. Pat. No. 3,492,330,
polyisocyanates which contain biuret groups as described e.g. in German
Pat. No. 1,101,394, in British Pat. No. 889,050 and in French Pat. No.
7,017,514, polyisocyanates which contain isocyanurate groups as described
e.g. in German Pat. Nos. 1,022,789 and 1,027,394 and in British Patent
Nos. 1,091,949, 1,267,011 and 1,305,036, polyisocyanates which contain
acylated urea groups according to U.S. Pat. No. 3,517,139 and
polyisocyanates which contain urethane groups as described e.g. in Belgian
Pat. No. 752,261 or in U.S. Pat. No. 3,394,164. Mixtures of the above
polyisocyanates maybe used. Organic polyisocyanates which are modified
with ionic groups for example, with carboxyl and/or carboxylate groups
and/or sulphonic acid groups and/or sulphonate groups may be used with the
polyisocyanates in this invention. Polyisocyanates may be reacted with
alkali metal silicates such as sodium metasilicate pentahydrate, potassium
metasilicate pentahydrate, dry granular crude sodium silicate, and dry
granular lithium silicate to produce polyisocyanate alkali metal silicate
prepolymer with terminal isocyanate groups or terminal alkali metal
silicate groups and may be used with the polyisocyanates in this
invention. The polyisocyanate is mixed with the dry granular alkali metal
silicate then heated to 30.degree. to 40.degree. C. while agitating at
ambient pressure for 10 to 30 minutes, thereby producing a polyisocyanate
prepolymer. Any of the suitable non-ionic hydrophilically modified organic
polyisocyanates may be used in this invention.
Suitable polyisocyanates such as the aromatic diisocyanates may be reacted
with organic compounds which contain at least two hydrogen atoms capable
of reacting with isocyanates, preferably with a molecular weight of
generally, from 300 to about 10,000 and in the ratio of from 50-99 mols of
aromatic diisocyanates with 1 to 50 mols of said organic compounds to
produce isocyanate-terminated reaction products. It is preferred to use
polyols (organic polyhydroxyl compounds), in particular compounds and/or
polymer which contain from 2 to 8 hydroxyl groups, especially those with a
molecular weight of from about 800 to about 10,000 and preferably from
1,000 to about 6,000, e.g. polyesters, polyethers, polythioethers,
polyacetals, polycarbonates, or polyester amides containing at least 2,
generally from 2 to 8, but preferably from 2 to 4 hydroxyl groups, of the
kind known for producing homogeneous and cellular polyurethanes. Compounds
which contain amino groups, thiol groups or carboxyl groups may be used.
Polyhydroxyl compounds, (polyols) which already contain urethane or urea
groups, modified or unmodified natural polyols, e.g. castor oil,
carbohydrates and starches may also be used. Addition products of alkylene
oxides with phenolformaldehyde resins or urea-form-aldehyde resins are
also suitable for the purpose of the invention. Polybutadiene polymers
with free hydroxyl groups, polysulfide polymers, polybutadiene-styrene
copolymers and butadiene-acrylonitrile copolymer chains are also suitable
for the purpose of the invention.
The hydroxyl group-containing polyesters (polyols) may be, for example,
reaction products of polyhydric alcohols, preferably dihydric alcohols and
polybasic, preferably dibasic carboxylic acids. The corresponding
polycarboxylic acid anhydride or corresponding polycarboxylic acid esters
of lower alcohols or their mixture may be used instead of the free
polycarboxylic acids for preparing the polyesters. The polycarboxylic acid
may be aliphatic, cycloaliphatic, aromatic, and/or heterocyclic and may be
substituted, e.g. with halogen atoms and may be unsaturated. Examples
include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic
acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic acid
anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid
anhydride, tetrachlorophthalic acid anhydride, glutaric acid anhydride,
maleic acid, maleic acid anhydride, fumaric acid, dimeric and trimeric
fatty acids such as oleic acid, optionally mixed with monomeric fatty
acids, dimethylterephthalate and bis-glycol terephthalate. Any suitable
polyhydric alcohol (polyol) may be used such as, for example, ethylene
glycol, propylene-1,2-and-1,3-glycol, butylene 1,4-and-2,3-glycol,
hexane-1, 6-diol, octane-1,8-diol, neopentyl glycol,
cyclohexanedimethol-(1,4-bis-hydroxy-methylcyclohexane),
2-methyl-propane-1, 3-diol, glycerol, trimethylol propane,
hexane-1,2,6-triol, butane-1,2,4-triol, trimethylol ethane,
pentaerythritol, quinitol, mannitol, sorbitol, glucose, starches,
fructose, cane sugar, dextrines, castor oils, methylglycoside, diethylene
glycol, triethylene glycol, tetraethylene-glycol, polyethylene glycols,
dipropyleneglycol, polypropylene glycols, dibutylene glycol and
polybutylene glycols. The polyesters may also contain a proportion of
carboxyl end groups. Polyesters of lactones, such as
.epsilon.-caprolactone, or hydroxy-carboxylic acids, such as
.omega.-hydroxy-caproic acid, may also be used.
The polyethers with at least 2, generally 2 to 8 and preferably 2 or 3
hydroxyl groups, used according to the invention are known and may be
prepared, e.g. by the polymerization of epoxides, e.g. ethylene oxide,
propyleneoxide, butylene oxide, tetrahydrofuran, styrene oxide, or
epichlorohydrin, each with itself, e.g. in the presence of BF.sub.3, or by
addition of these epoxides, optionally as mixtures or successively, to
starting components which contain reactive hydrogen atoms such as alcohols
or amines, e.g. water, ethylene glycol, propylene-1,3-or-1,2-glycol,
trimethylol propane, 4,4'-dihydroxydiphenylpropane, aniline, ammonia,
ethanolamine or ethylenediamine. Sucrose polyethers such as those
described, e.g. in German Pat. Nos. 1,176,358 and 1,064,938 may also be
used according to this invention. It is frequently preferred to use
polyethers which contain predominantly primary OH groups, (up to 90% by
weight, based on the total OH group content of the polyether). Polyethers
modified with vinyl polymers such as those which may be obtained by
polymerizing styrene or acrylonitrite in the presence of polyethers, (U.S.
Pat. Nos. 3,383,351; 3,304,273; 3,525,093 and 3,110,695 and German Pat.
No. 1,152,536), and polybutadienes which contain contain OH groups are
also suitable.
By "polythioethers" are meant, in particular, the condensation products of
thiodiglycol with itself and/or with other glycols, dicarboxylic acids,
formaldehyde, aminocarboxylic acids or amino alcohols. The products
obtained are polythio-mixed ethers, polythioether esters or polythioether
ester amides, depending on the cocomponent.
The polyacetals used may be for example, the compounds which may be
obtained from glycols, e.g. diethylene glycol, triethylene glycol,
4,4'-dihydroxydiphenyldimethylmethane, hexanediol and formaldehyde.
Polyacetals suitable for the invention may also be prepared by the
polymerization of cyclic acetals.
The polycarbonates with hydroxyl groups used may be of the known kind, e.g.
those which may be prepared by reacting diols, e.g. propane-1,3-diol,
butane-1,4 diol and/or hexane-1,6-diol or diethylene glycol, triethylene
glycol or tetraethylene glycol, with diarylcarbonates, e.g.
diphenylcarbonate or phosgene.
The polyester amides and polyamides include, e.g. the predominantly linear
condensates obtained from polyvalent saturated and unsaturated carboxylic
acids or their anhydrides and polyvalent saturated and unsaturated amino
alcohols, diamines, polyamines and mixtures thereof.
Examples of these compounds which are to be used according to the invention
have been described e.g. in High Polymers, Vol. XVI, "Polyurethanes,
Chemistry and Technology", published by Saunders-Frisch, Interscience
Publishers, New York, London, Volume I, 1962, pages 32 to 42 and pages 44
to 54 and Volume II 1964, pages 5 to 6 and 198 to 199 and in
Kunststoof-Handbuch, Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag,
Munich, 1966, e.g. on pages 45 to 71.
Suitable modified organic polyisocyanates, as well as their propolymers,
especially those based on aromatic polyisocyanates, can also be
subsequently modified to give ionic groups, for example by reaction with
sulphones, beta-lactones, by grafting on acrylic acid, methacrylic acid or
crotonic acid, for example, or by sulphuric acid, chlorosulphonic acid,
oleum or sulphur trioxide and used in the invention. In particular,
organic polyisocyanates such as tolylene diisocyanate, diphenylmethane
diisocyanate, hexamethylene diisocyanate, and the known phosgenation
products of the condensation products of aromatic monoamines, especially
aniline and aldehyde, especially formaldehyde, reacted with sulphuric
acid, oleum or sulphur trioxide may be used in this invention. Sulphonated
polyisocyanates of this kind which generally still contain urethane, urea,
and biuret groups, and in particular where polyol modification has been
carried out before sulphonation, urethane-and/or allophanate groups which
are formed through secondary reactions during sulphonation are therefore
particularly preferred as polyisocyanates containing ionic groups. The NCO
terminated prepolymers used, for example for the production of aqueous
polyurethane dispersions (U.S. Pat. No. 3,756,992) can be used for the
process according to the invention.
Component C
Component (C) contains organic amphiphilous compounds, preferably contain
from 1 to 9 carbon atoms and has a molecular weight of from 32 to about
400, preferably from 32 to 150, which contain one OH group and/or at least
one other hydrophilic and/or polar group. The other hydrophilic and/or
polar group is preferably a functional group corresponding to one of the
following general formulae: RSH, RCH.sub.2 Cl, RCH.sub.2 Br, RCH.sub.2 I,
RCN, RNO.sub.2, RCOCl, RCOBr, RSO.sub.2 Cl, RCOOH, RSO.sub.3 H,
RCOO.sup.-, RSO.sub.3.sup.-, ROR,
##STR1##
wherein R denotes a methyl, ethyl or propyl group. The organic
amphilphilous compounds of component C may contain an OH group and/or from
1 to 6, preferably 1 or 2 of these other functional groups.
The following are examples of component (C):
1. alcohols, thioalcohols, phenols and thiophenols:
methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butyl
alcohol and the isomeric pentanols, hexanols and heptanols, cyclohexanol,
methylcyclohexanol, allyl alcohol methallyl alcohol, cyclohexano-methanol,
benzyl alcohol, butylmercaptan, phenols, e.g. phenol and the cresols,
thiophenols and thiocresols. Alcohols with from 1 to 4 carbon atoms are
preferred, particularly methanol.
2. Aldehydes:
Formaldehyde, acetaldehyde, propionaldehyde, butyl aldehyde, pentanals,
hexanals, heptanals, octanals and their simple substitution products,
semi-acetals and full acetals.
3. Carboxylic acids:
Formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid,
pentanoic acid, hexane carboxylic acid, heptane carboxylic acid,
cyclohexane carboxylic acid, benzoic acid, toluic acid.
4. Carboxylic acid chlorides, carboxylic acid bromides, sulphonic acid
chlorides:
Acetyl chloride, propionic acid chloride, acetyl bromide, acid chlorides of
C.sub.4 -C.sub.6 monocarboxylic acids, but also methanesulphonic acid
chloride, benzenesulphonic acid chloride, p-toluenesulphochloride,
o-toluenesulphochloride, carbamic acid chlorides, e.g. t-butyl carbamic
chloride, and phenylcarbamic chloride.
5. Esters:
Methyl acetate, ethyl acetate, propylacitate, butyl acetate, amyl acetate,
the methyl and ethyl esters of propionic, butyric, pentanoic, hexanoic and
heptanoic acid and the corresponding isomeric compounds, for example
isobutyric acid, and 2,4,6-tribromophenylacetate.
6. Ethers and Thioethers:
Methyl ethyl ether, cyclohexyl methyl ether, methyl butyl ether, phenol
methyl ether, thiophenol methyl ether, cresol methyl ether,
tetrahydrofuranomethyl-methyl ether.
7. Halomethyl compounds:
Ethyl chloride, ethyl bromide, ethyl iodide, n-propylchloride,
n-propylbromide, n-propyliodide, isopropyl chloride, isopropyl bromide,
isopropyl iodide, butyl chloride, butyl bromide, butyl iodide, C.sub.3
-C.sub.6 -halogenated methyl compounds, benzylhalides e.g. benzylchloride
or benzylbromide, hexahydrobenzyl halides, e.g. cyclohexanomethyl
chloride, epichlorohydrin, 2-ethyl-2-chloromethyloxetane and
2-ethyl-2-chloro-methyloxetane. Halogenated methyl compounds which contain
from 4 to 7 carbon atoms are preferred.
8. Ketones:
Methyl ethyl ketone, methyl-isopropyl ketone, methyl-isobutyl ketone,
methyl-isoamyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone,
methyl-t-butyl ketone, methyl-furanyl ketone, methyl-tetrahydrofuranyl
ketone, methyl-heptyl ketone, ethylhexyl ketone, acetaphonone,
.omega.-chloroacetophenone and propiophenone.
9. Nitriles:
Acetonitrile, propionitrile, butyronitrile, tolunitrile,
hexahydrobenzonitrile, acrylonitrile, allylnitrile, methallylnitrile,
methacrylonitrile.
10. Nitro compounds:
Nitromethane, nitroethane, nitrohexane, nitrobenzene, chlorinated
nitrobenzenes, nitro-cyclohexanes, brominated nitrobenzenes, benzyl
nitrate and nitrotoluene.
11. Sulphonic acids:
Methanesulphonic acid, ethanesulphonic acid, butanesulphonic acid,
benzenesulphonic acid, 2-toluenesulphonic acid, 4-toluenesulphonic acid,
chlorosulphonic acid esters and sulphonic acid esters e.g.
methanesulphonic acid methyl ester, methane sulphonic acid ethyl ester and
chlorosulphonic acid methyl ester.
The carboxyl acids and/or sulphonic acids may be partially or completely
neutralized, for example with alkali metal and alkaline earth metal
hydroxides e.g. sodium hydroxide, potassium hydroxide, barium hydroxide,
or magnesium hydroxide, or by the addition of amines, e.g. trimethylamine,
triethylamine, methylmorpholine, pyridine, dimethylaniline, or metal
alcoholates e.g. sodium t-butanolate or potassium isopropanolate. Metal
oxides, hydroxides or carbonates, either in the solid form or suspended in
diluents, may also be used for neutralization. Calcium oxide, magnesium
oxide, calcium carbonate, magnesium carbonate and dolomite, for example,
are particularly suitable. Tertiary amines are useful in this
neutralization, e.g. alkoxylated products of primary and secondary amines,
and also polyesters or polyacrylates which contain tertiary nitrogen atoms
as well as the known condensation products based on epichlorohydrin and
polyamines.
12. Components (C) according to this invention may also comprise compounds
which contain phosphorus, for example, trimethyl phosphite,
trimethylphosphates, triethylphosphite, triethyl phosphate,
diethylphosphite, diethylphosphate, dimethylphosphite, dimethylphosphate,
thiophosphoric acid-O, O-dimethylester, thiophosphoric acid
trimethylester, or theophosphoric acid-O, O-dimethyl ester chloride.
13. Lignin:
Calcium lignosulfonate, lignosulfonic acid sodium salts, lignosulfonic
acid, lignin sulfate produced by the alkali process (Kraft's process) and
particularly de-sulfonated lignin.
Component D
Component (D) contains the curing agents and/or activators. The following
are examples of Component D:
1. water.
2. Water containing 10% to 70% by weight of an alkali metal silicate, such
as sodium and/or potassium silicate. Crude commercial alkali metal
silicate may contain other substances, e.g. calcium silicate, magnesium
silicate, borates or aluminates and may also be used. The molar ratio of
Ml.sub.2 OSiO.sub.2 (Ml=metal) is not critical and may vary within the
usual limits but is preferably between 4 to 1 and 0.2 to 1.
3. Water containing 20 to 50% by weight of ammonium silicate.
4. Water containing 5% to 40% by weight of magnesium oxide in the form of a
colloidal dispersion.
5. Alkali metal metasilicate pentahydrate such as sodium, commercial dry
granular sodium and potassium silicates, and potassium metasilicate
pentahydrate.
6. Water containing 20% to 70% by weight of silica sol.
7. Water containing 0.001% to 10% by weight of an activator (catalyst) such
as
(a) tertiary amines, e.g. triethylamine, tributylamine,
N-methyl-morpholine, N-ethyl-morpholine, N-coco-morpholine,
N,N,N',N'-tetramethylethylenediamine, 1,4-diazo-bicyclo-(2,2,2)-octane,
N-methyl-N'-dimethylaminoethyl piperazine,N,N-dimethylbenzylamine,
bis(N,N-diethylaminoethyl)-adipate, N,N-diethylbenzylamine,
pentamethylenetriamine, N,N-dimethylcyclohexylamine,
N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethyl-1,3-butanediamine,
N,N-dimethylbeta-phenylethylamine and, 1,2-dimethylimidazole. Suitable
tertiary amine activators which contain hydrogen atoms which are reactive
with isocyanate groups include, e.g. triethanolamine, triisopanolamine,
N,N-dimethylethanolamine, N-methyl-diethanolamine, N-ethyldiethanolamine,
and their reaction products with alkylene oxides, e.g. propylene oxide
and/or ethylene oxide.
(b) Organo-metallic compounds, preferably organo-tin compounds such as tin
salts of carboxylic acids, e.g. tin acetate, tin octoate, tin ethyl
hexoate, and tin laurate and the dialkyl tin salts of carboxylic acids,
e.g. dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or
diocyl tin diacetate.
(c) Silaamines with carbon-silicon bonds as described e.g. in British Pat.
No. 1,090,589, may also be used as activators, e.g.
2,2,4-trimethyl-2-silamorpholine or
1,3-diethylaminomethyl-tetramethyl-disiloxane.
(d) Other examples of catalysts which may be used according to the
invention and details of their action are described in
Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,
Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 96 and 102.
8. Water containing 20% to 70% by weight of a water-binding agent being
capable of absorbing water to form a solid or a gel, such as hydraulic
cement, synthetic anhydrite, gypsum or burnt lime.
9. Water containing 1% to 10% by weight of bases which contain nitrogen
such as tetraalkyl ammonium hydroxides.
10. Water containing 1% to 10% by weight of alkali metal hydroxides such as
sodium hydroxide, alkali metal phenolates such as sodium phenolate or
alkali metal alcoholates such as sodium methylate.
11. Water containing sodium polysulfide in the amount of 1% to 10% by
weight.
Surface active additives, (emulsifiers and foam stabilizers) may also be
used according to the invention. Suitable emulsifiers are e.g. the sodium
salts of ricinoleic sulphonates or of fatty acids, or salts of fatty acids
with amines, e.g. oleic acid diethylamine or stearic acid diethanolamine.
Other surface active additives are alkali metal or ammonium salts of
sulphonic acids, e.g. dodecylbenzene sulphonic acid or dinaphthyl methane
disulphonic acid, or of fatty acids e.g. ricinoleic acid, or of polymeric
fatty acids.
The foam stabilizers used are mainly water-soluble polyester siloxanes.
These compounds generally have a polydimethylsiloxane group attached to a
copolymer of ethylene oxide and propylene oxide. Foam stabilizers of this
kind have been described e.g. in U.S. Pat. No.3,629,308. These additives
are preferably used in quantities of from 0% to 20%, by weight, based on
the reaction mixture.
Negative catalysts, for example, substances which are acidic in reaction,
e.g. hydrochloric acid or organic acid halides, known cell regulators,
e.g. paraffins, fatty alcohols or dimethyl polysiloxanes, pigments or
dyes, known flame retarding agents, e.g. tris-chlorethylphosphate or
ammonium phosphate and polyphosphates, stabilizers against aging and
weathering, plasticizers, fungicidal and bacteriocidal substances and
fillers, e.g. barium sulphate, kieselguhr, carbon bla | | |
