CA2125155A1 - Process for the production of rigid foams containing urethane groups - Google Patents
Process for the production of rigid foams containing urethane groupsInfo
- Publication number
- CA2125155A1 CA2125155A1 CA002125155A CA2125155A CA2125155A1 CA 2125155 A1 CA2125155 A1 CA 2125155A1 CA 002125155 A CA002125155 A CA 002125155A CA 2125155 A CA2125155 A CA 2125155A CA 2125155 A1 CA2125155 A1 CA 2125155A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- groups
- mixture
- isocyanate
- polyisocyanates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/727—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80 comprising distillation residues or non-distilled raw phosgenation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
Abstract
Process for the production of rigid foams containing urethane groups A b s t r a c t Rigid foams containing urethane groups and optionally isocyanurate groups are produced by the reaction of a) sump products containing isocyanate groups and having a tolylenediisocyanate content of less than 5 % b.w., preferably less than 200 ppm (weight) obtainable from A) distillation residues of tolylenediisocyanate production by mixing the distillation residues A) with B) polyisocyanates or polyisocyanate mixtures of the diphenylmethane series optionally modified with urethane and/or allophanate groups and having an isocyanate content of at least 15% by weight and working up of the mixture by distillation, the mixture being heated to temperatures from 190 to 250°C before or during the distillative working up, whereby the tolylene diisocyanate which is reversibly bound in distillation residue A) undergoes substantial substitution by polyisocyan-ate B), with b) compounds in the molecular weight range of from 400 to 10,000 having at least two isocyanate reactive hydrogen atoms in the presence of c) water and/or readily volatile organic substances as blowing agents and optionally in the presence of d) compounds in the molecular weight range of from 32 to 399 having at least two isocyanate reactive hydrogen atoms and e) auxiliary agents and additives known per se.
Description
- -' 212~
Process for the production of rigid foams containing urethane groups This invention relates to a process for the production of 5 rigid polyurethane foams or rigid polyurethane foams having isocyanurate structures, using mixtures of distillation residues of tolylene diisocyanate (TDI) production and polyisocyanates of the diphenylmethane series.
10 The production of tolylene diisocyanate (TDI) by the phosgenation of tolylene diamine on a technical scale gives rise to relatively high molecular weight compounds having uretdione, isocyanurate, carbodiimide, uretone-imine, urea and biuret structures, which are obtained as15 tarry masses when the reaction mixture is distilled. This distillation residue, which may still have a relatively high residual isocyanate content, is not suitable for the usual isocyanate applications (e.g. the production of polyurethanes~. No suitable processes by which the 20 distillation residue can- be converted into an isocyanate component suita}~le for the production of polyurethane foams have hitherto been described in the technical literature. Processes described in US-PS 3 634 361, DE-OS
Process for the production of rigid foams containing urethane groups This invention relates to a process for the production of 5 rigid polyurethane foams or rigid polyurethane foams having isocyanurate structures, using mixtures of distillation residues of tolylene diisocyanate (TDI) production and polyisocyanates of the diphenylmethane series.
10 The production of tolylene diisocyanate (TDI) by the phosgenation of tolylene diamine on a technical scale gives rise to relatively high molecular weight compounds having uretdione, isocyanurate, carbodiimide, uretone-imine, urea and biuret structures, which are obtained as15 tarry masses when the reaction mixture is distilled. This distillation residue, which may still have a relatively high residual isocyanate content, is not suitable for the usual isocyanate applications (e.g. the production of polyurethanes~. No suitable processes by which the 20 distillation residue can- be converted into an isocyanate component suita}~le for the production of polyurethane foams have hitherto been described in the technical literature. Processes described in US-PS 3 634 361, DE-OS
2 123 183, DE-OS 2 333 150, US-PS 3 634 361 and DE-OS
25 2 423 594, for example, use organic solvents in the Le A 28 829 3 .~ . .... .
2 1 2 ~
presence of monomeric diisocyanates, whereby the useful~
ness of the mixtures is greatly diminished. Storage stak,ility and possibility of standardization of the solutions are entirely inadequate (sedimentation of insc>luble substances).
It was an object of this invention to provide a process with which rigid polyurethane foams of sufficient quality cou:Ld be produced from the residue of the distillation of tol~ylene diisocyanate (produced by the phosgenation of tolylene diamine).
The present invention relates to a process for the production of rigid foams containing urethane and optionally isocyanurate groups by the reaction of a) polyisocyanates with 5 b) compounds in the molecular weight range of from 400 to 10,000 containing at least two isocyanate reactive hydrogen atoms, in the presence of ~ ! , , .
c) water and/or readily volatile organic substances as blowing agents, and optionally in the presence of ~ :
t) d) compounds in the molecular weight range of from 32 to 399 having at least two isocyanate reactive hydrogen atoms, and e) auxiliary agents and additives known per se, characterised in that the polyisocynate a) used is a sump product containing isocyanate groups and having a tolylene diiisocyanate content of less than 5 % b.w., preferably less than 1 % b. w., more preferably~ .
Iess than 200 ppm (weight), obtaiinable from A) distillation residues of the productiion .. . .. ...... . . . . . .. ... .
212~15~
of tolylene diisocyanate by mixing the distillation residues A) with B) polyisocyanates or polyioscyanate mixtures of the diphenylmethane series optionally modified wit:h urethane and/or allophanate groups and having an isocyanate content of at least 15% by weight and working up the mixture by distillation, the mixture being heated to temperatures of from 190 to 250C before or during the distillative working up, whereby the tolylene diisocyanate which is reversibly bound in distillation residue A) undergoes substantial substitution by polyisocyanate B).
According to the invention, it is preferred - 1o use, as component B), 4,4'-diisocyanatodiphenyl-methane, its commercial mixtures with 2,4'- and optionally 2,2'-diisocyanatodiphenylmethane or mixtures of these diisocyanatodiphenylmethane isomers with up to l;5% by weight, based on the mixture, of their higher homologues containing more than 2 isocyanate groups per molecule, :
- 1to use isocyanate group-containing sump products to which from 20 to 80~ by weight, preferably from 40 to :
~50% by weight of polyisocyanates of the diphenylmethane ;::
series have been added, and - to add, as polyisocyanates of the diphenylmethane ~series, mixtures of the diisocyanatodiphenylmethane .isomers with up to 65% by weight (based on the mixture) of their higher homologues containing more than 2~ iso- ~ :
,cyanate groups per molecule.
It was surprisingly found that the above-mentioned sump product could easily be standardiz~d and used for the : :~
production of rigid polyurethane foams with satisfactory Le A 28 829 5 :
`' '' ''~
-:
, ,, . ~ . ....... . ... ~
212~5~
properties in spite of the heat treatment. The low proportion of free TDI, wh;ch is often less than 200 ppm, is a particular advantage on toxicological and physiological grounds. The sump products have a viscosity of from 200 to 10,000 mPa.s at 25~C and an isocyanate content of from 23 to 31% by weight, depending on the type and quantity of the polyisocyanate of the diphenylmethane series used.
The following are used for the production of the foams ¦
containing urethane groups and optionally isocyanurate ¦
10 groups:
a) as starting components, the above-mentioned isocyanate group-containing sump products to be used according to the invention.
The following are optionally used in addition as polyisocyanate starting components (in quantities of up to 60% by weight):
aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates as described e.g.
by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those correspond-ing to the formula Q(NC0)n wherein n =2-4, preferably 2-3, and Q denotes an aliphatic hydrocarbon group having 2-18, preferably 6-10 carbon atoms, a cycloaliphatic hydrocarbon yroup having 4-15, preferably 5-10 carbon atoms, an aromatic hydrocarbon group having 6-15, preferably 6-13 carbon atoms or an aralipha-Le A 28 829 6 ., . ~ ..... . .
21251~
tic hydrocarbon g~oup having 8-15, preferably 8-13 carbon atoms, e.g. polyisocyanates of the type described in DE-OS 28 32 253, pages lo-ll. It is generally particularly preferred to use the commercially readily available polyisocyanates, e.g. 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"); polyphenylpoly-methylene polyisocyanates prepared by aniline-formaldehyde condensation followed by phosgenation ("crude MDI") and polyisocyanates containing carbo-diimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("modified polyisocyanates"), in particular those modified polyisocyanates which are derived from 2,4- and/or 2,6-tolylene diisocyanate or from 4,4'- and/or 2,~'-diphenylmethane diisocyanate.
b) Compounds generally in the molecular weight range of from 400 to 10,000 having at least two isoryan-ate reactive hydrogen atoms are also used as starting components. These may be compounds containing amino groups, thio groups or carboxyl ~ :
groups but are preferably compounds containing ~ ~ .
hydroxyl groups, in particular compounds having 2 to 8 hydroxyl groups, especially those having molecular weights of from 1000 to 6000, preferably -:
from 2000 to 6000, e.g. the polyethers, polyesters, polycarbonates and polyester amides having at least 2, generally 2 to 8, preferably 2 to 6 hydroxyl ~ : :
groups known per se for the production of both homogeneous and cellular polyurethanes and :
described e.g. in DE-OS 28 32 253, pages 11-18.
c) Water and/or readily volatile organic substances known per se are used as blowing agents, preferably Le A 28 829 7 -:~ :
.
21~5155 pentane, isopentane and cyclopentane.
d) Compounds in the molecular weight range of from 32 to 399 having at least two isocyanate reactive hydrogen atoms may also be used as starting components. These compounds are also understood to be compounds containing hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds containing hydroxyl groups and/or amino groups, which serve as chain lengthening agents or cross-linking agents. These compounds generally have from 2 to 8, preferably 2 to 4 isocyanate reactive hydrogen atoms. Examples are described in DE-OS 28 32 253, pages 19-20.
e) Auxiliary agents and additives are optionally used, such as - catalysts of known type in ~uantities of up to 10% by weight, based on component b), - surface active additives such as emulsifiers and foam stabilizers, 2() - reaction retarders, e.g. substances which are acid in reaction such as hydrochloric acid or organic acid halides, cell regulators known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments and 2'5 dyes, flame retardants known per se, e.g. tri-cresyl phosphate, stabilizers against ageing and weathering, plasticizers, fungistatic and bacteriostatic substances and fillers such as barium sulphate, kieselguhr, carbon black or whiting.
Le A 28 829 8 212~15~
These auxiliary agents and additives optionally used are described, for example, in DE-OS 27 32 292, pages 21-24.
Further examples of additives optionally used according to the invention, such as surface-active additives and foam stabilizers, cell regulators, reaction retarders, stabilizers, flame retardants, plasticizers, dyes, fillers and fungistatic and bacteriostatic substances and details concerning their use and mode of action are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103-113.
Method of carrying out the process for the production of polyurethane plastics:
The components are reacted together by the known one-shot process, prepolymer process or semi-prepolymer process, in many cases using mechanical devices such as those described in US-PS 27 64 565. Details concerning the processing apparatus suitable for the invention are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g.
on pages 121 to 205.
The foams may, of course, also be produced by block foaming or by the laminator process known per se.
The~ products obtainable according to the invention may be used e.g. as insulating boards for roof insulation.
Le A 28 829 9 .... ...... . .. . .
2~2 ~
Examples Preparation of the sump products Sump product I:
A mixture of 4.4 parts by weight of TDI distillation resi~ue and 5.4 parts by weight of diisocyanatodiphenyl-methane was preheated to 90 C and continuously introduced into the reactor of a continuously operating laboratory distillation plant and heated therein to 2000c. The TDI
distillation residue, containing about 65% by weight of lo dissolved TDI which could be split off by heat, had been obt.ained by the phosgenation of tolylene diamine (80% by wei.ght 2,4-isomer and 20% by weight of 2,6-isomer) in dic:hlorobenzene followed by distillation. The diisocyan-atcl-diphenylmethane was an isomeric mixture of 93.7% by weight of 4,4'-diisocyanato-diphenylmethane, 6.1% by wei.ght of 2,4'-diisocyanato-diphenylmethane and 0~2% by wei.ght of 2,2'-diisocyanato-diphenylmethane.
The sump product contained about 45 ppm (weight) of free TD]: and had a viscosity of 335 mPa.s at 25C and an iso-cyanate content of 28.4%.
Surnp product II:
The starting material used consisted of a mixture of 2.5parts by weight of TDI distillation residue and 5.5 parts by weight of a polyisocyanate consisting of 45.0% by weight of 4,4'-diisocyanato-diphenylmethane, 2.3% by we:ight of 2,4'-diisocyanatodiphenylmethane and about 50%
by weight of higher homologues of diisocyanatodiphenyl-methane containing more than 2 isocyanate groups per mo:Lecule.
.
Le A 28 829 10 . , .. ,.. , ..... ... .......... . . . , .. , .. ..... ~ . .. ....
f ~-` 212~1~5 .
The sump product obtained contained 5S ppm (weiyht) of ;
free TDI and had a viscosity of 4700 mPa.s at Z5C and an isocyanate content of 27.8%.
Preparation of polyurethane foams:
The so-called hand mixing process was employed for producing the PUR rigid foam in the following Examples.
A ~antity of about l kg was prepared in each case from the! polyol mixture without blowing agent and was tempered at 20-C in closed containers in a so-called air condition-ing cupboard. The test foams were prepared from about 300g of reaction mixture. For this purpose, the appropriate quantity of the polyol mixture was first weighed into a paper cup with metal base (diameter about 9 cm, height about 14 cm) and the blowing agent was added. Mixing was carried out with an electrically driven disc stirrer (about lO00 revs/min). The loss of blowing agent was de1:ermined by back weighing and replaced. The quantity of isocyanate required for the formulation was then added and the mixture was stirred for lO to 15 seconds.
After the components had been mixed, the reaction mixture was immediately poured into a box made of wrapping paper having a base of 20 x 20 cm2 and a height of 14 cm to produce a so-called test pack foam. The reaction times (e.g. gel time) were measured on the foam which was being produced. The gross density was determined on the finished foam.
Foam blocks measuring 24 cm x 24 cm x 8.0 cm were produced to test the properties of the foams. A laboratory book-binding press whose press plates (aluminium) had been tempered to 35-C by water flowing through them was used for this purpose. An aluminium frame which had the Le A 28 829 ll ... , . ' ~
2125155 :
internal dimensions 24 cm x 24 cm x 8.0 cm and had been preheated to 35~C was placed on the lower plate of the open press. A box made of wrapping paper and having the same external dimensions was placed in the frame and the reaction mixture was poured in. A sheet of wrapping paper was placed on the frame and the press was closed. The foam body was removed after about 30 minutes.
Le A 28 829 12 ....... . . ~
-- 2~2~1~5 : ~
Exam~le 1 ~
Pre!paration of a polyurethane foam expanded by means of ~;
monofluorotrichloromethane (R 11) 1.8 Parts by weight of water, 2.6 parts by weight of N,N-dimethyl-cyclohexylamine as reaction accelerator, 1.6 parts by weight of foam stabilizer Tegostab 8404 (Th.
Goldschmidt Company) and 38 parts by weight of blowing agent R 11 were added to 85 parts by weight of a polyether polyol prepared by the propoxylation of saccharose and ethylene glycol (molar ratio 2:1) with OH 460 and the components were mixed by stirring. This mixture was then stirred up with 135 parts by weight of sump product I. The initially brittle foam was tough after about l hour.
Foaming data: Stirring time 10 s Resting time 15 s Gel time 7S s free gross density 21 kg/m3 A sample in the form of a foam plate 80 mm in thickness and having a gross density of 45 kg/m3 was found to have undergone the following changes in dimension after 48 hours' storage at 70C (dimensional stability according to DIlt 18 164 Part 1):
Length: -0.14 %
Width: -0.54 %
Thickness: -1.99 %.
Le A 28 829 13 O~; ~ ~ ~ ,,, 212~
Example 2 Production of a polyurethane foam expanded by means of water/difluoromonochloromethane (R 22) The following polyol mixture was first prepared in a be;~ker: 40 Parts by weight of propoxylated glycerol with OH number 250, 30 parts by weight of propoxylated sacchar-ose/propylene glycol mixture with OH number 380 (viscosity at 25C: 13,000 mPa.s), 9.4 parts by weight of propoxyl-ated triethanolamine, OH number 150, 20.6 parts by weight of propoxylated triethanolamine, OH number 500, and 10 pa,rts by weight of propoxylated sorbitol, OH number 1390, containing 33% by weight of ethylene glycol.
25 2 423 594, for example, use organic solvents in the Le A 28 829 3 .~ . .... .
2 1 2 ~
presence of monomeric diisocyanates, whereby the useful~
ness of the mixtures is greatly diminished. Storage stak,ility and possibility of standardization of the solutions are entirely inadequate (sedimentation of insc>luble substances).
It was an object of this invention to provide a process with which rigid polyurethane foams of sufficient quality cou:Ld be produced from the residue of the distillation of tol~ylene diisocyanate (produced by the phosgenation of tolylene diamine).
The present invention relates to a process for the production of rigid foams containing urethane and optionally isocyanurate groups by the reaction of a) polyisocyanates with 5 b) compounds in the molecular weight range of from 400 to 10,000 containing at least two isocyanate reactive hydrogen atoms, in the presence of ~ ! , , .
c) water and/or readily volatile organic substances as blowing agents, and optionally in the presence of ~ :
t) d) compounds in the molecular weight range of from 32 to 399 having at least two isocyanate reactive hydrogen atoms, and e) auxiliary agents and additives known per se, characterised in that the polyisocynate a) used is a sump product containing isocyanate groups and having a tolylene diiisocyanate content of less than 5 % b.w., preferably less than 1 % b. w., more preferably~ .
Iess than 200 ppm (weight), obtaiinable from A) distillation residues of the productiion .. . .. ...... . . . . . .. ... .
212~15~
of tolylene diisocyanate by mixing the distillation residues A) with B) polyisocyanates or polyioscyanate mixtures of the diphenylmethane series optionally modified wit:h urethane and/or allophanate groups and having an isocyanate content of at least 15% by weight and working up the mixture by distillation, the mixture being heated to temperatures of from 190 to 250C before or during the distillative working up, whereby the tolylene diisocyanate which is reversibly bound in distillation residue A) undergoes substantial substitution by polyisocyanate B).
According to the invention, it is preferred - 1o use, as component B), 4,4'-diisocyanatodiphenyl-methane, its commercial mixtures with 2,4'- and optionally 2,2'-diisocyanatodiphenylmethane or mixtures of these diisocyanatodiphenylmethane isomers with up to l;5% by weight, based on the mixture, of their higher homologues containing more than 2 isocyanate groups per molecule, :
- 1to use isocyanate group-containing sump products to which from 20 to 80~ by weight, preferably from 40 to :
~50% by weight of polyisocyanates of the diphenylmethane ;::
series have been added, and - to add, as polyisocyanates of the diphenylmethane ~series, mixtures of the diisocyanatodiphenylmethane .isomers with up to 65% by weight (based on the mixture) of their higher homologues containing more than 2~ iso- ~ :
,cyanate groups per molecule.
It was surprisingly found that the above-mentioned sump product could easily be standardiz~d and used for the : :~
production of rigid polyurethane foams with satisfactory Le A 28 829 5 :
`' '' ''~
-:
, ,, . ~ . ....... . ... ~
212~5~
properties in spite of the heat treatment. The low proportion of free TDI, wh;ch is often less than 200 ppm, is a particular advantage on toxicological and physiological grounds. The sump products have a viscosity of from 200 to 10,000 mPa.s at 25~C and an isocyanate content of from 23 to 31% by weight, depending on the type and quantity of the polyisocyanate of the diphenylmethane series used.
The following are used for the production of the foams ¦
containing urethane groups and optionally isocyanurate ¦
10 groups:
a) as starting components, the above-mentioned isocyanate group-containing sump products to be used according to the invention.
The following are optionally used in addition as polyisocyanate starting components (in quantities of up to 60% by weight):
aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates as described e.g.
by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those correspond-ing to the formula Q(NC0)n wherein n =2-4, preferably 2-3, and Q denotes an aliphatic hydrocarbon group having 2-18, preferably 6-10 carbon atoms, a cycloaliphatic hydrocarbon yroup having 4-15, preferably 5-10 carbon atoms, an aromatic hydrocarbon group having 6-15, preferably 6-13 carbon atoms or an aralipha-Le A 28 829 6 ., . ~ ..... . .
21251~
tic hydrocarbon g~oup having 8-15, preferably 8-13 carbon atoms, e.g. polyisocyanates of the type described in DE-OS 28 32 253, pages lo-ll. It is generally particularly preferred to use the commercially readily available polyisocyanates, e.g. 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"); polyphenylpoly-methylene polyisocyanates prepared by aniline-formaldehyde condensation followed by phosgenation ("crude MDI") and polyisocyanates containing carbo-diimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("modified polyisocyanates"), in particular those modified polyisocyanates which are derived from 2,4- and/or 2,6-tolylene diisocyanate or from 4,4'- and/or 2,~'-diphenylmethane diisocyanate.
b) Compounds generally in the molecular weight range of from 400 to 10,000 having at least two isoryan-ate reactive hydrogen atoms are also used as starting components. These may be compounds containing amino groups, thio groups or carboxyl ~ :
groups but are preferably compounds containing ~ ~ .
hydroxyl groups, in particular compounds having 2 to 8 hydroxyl groups, especially those having molecular weights of from 1000 to 6000, preferably -:
from 2000 to 6000, e.g. the polyethers, polyesters, polycarbonates and polyester amides having at least 2, generally 2 to 8, preferably 2 to 6 hydroxyl ~ : :
groups known per se for the production of both homogeneous and cellular polyurethanes and :
described e.g. in DE-OS 28 32 253, pages 11-18.
c) Water and/or readily volatile organic substances known per se are used as blowing agents, preferably Le A 28 829 7 -:~ :
.
21~5155 pentane, isopentane and cyclopentane.
d) Compounds in the molecular weight range of from 32 to 399 having at least two isocyanate reactive hydrogen atoms may also be used as starting components. These compounds are also understood to be compounds containing hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds containing hydroxyl groups and/or amino groups, which serve as chain lengthening agents or cross-linking agents. These compounds generally have from 2 to 8, preferably 2 to 4 isocyanate reactive hydrogen atoms. Examples are described in DE-OS 28 32 253, pages 19-20.
e) Auxiliary agents and additives are optionally used, such as - catalysts of known type in ~uantities of up to 10% by weight, based on component b), - surface active additives such as emulsifiers and foam stabilizers, 2() - reaction retarders, e.g. substances which are acid in reaction such as hydrochloric acid or organic acid halides, cell regulators known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments and 2'5 dyes, flame retardants known per se, e.g. tri-cresyl phosphate, stabilizers against ageing and weathering, plasticizers, fungistatic and bacteriostatic substances and fillers such as barium sulphate, kieselguhr, carbon black or whiting.
Le A 28 829 8 212~15~
These auxiliary agents and additives optionally used are described, for example, in DE-OS 27 32 292, pages 21-24.
Further examples of additives optionally used according to the invention, such as surface-active additives and foam stabilizers, cell regulators, reaction retarders, stabilizers, flame retardants, plasticizers, dyes, fillers and fungistatic and bacteriostatic substances and details concerning their use and mode of action are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103-113.
Method of carrying out the process for the production of polyurethane plastics:
The components are reacted together by the known one-shot process, prepolymer process or semi-prepolymer process, in many cases using mechanical devices such as those described in US-PS 27 64 565. Details concerning the processing apparatus suitable for the invention are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g.
on pages 121 to 205.
The foams may, of course, also be produced by block foaming or by the laminator process known per se.
The~ products obtainable according to the invention may be used e.g. as insulating boards for roof insulation.
Le A 28 829 9 .... ...... . .. . .
2~2 ~
Examples Preparation of the sump products Sump product I:
A mixture of 4.4 parts by weight of TDI distillation resi~ue and 5.4 parts by weight of diisocyanatodiphenyl-methane was preheated to 90 C and continuously introduced into the reactor of a continuously operating laboratory distillation plant and heated therein to 2000c. The TDI
distillation residue, containing about 65% by weight of lo dissolved TDI which could be split off by heat, had been obt.ained by the phosgenation of tolylene diamine (80% by wei.ght 2,4-isomer and 20% by weight of 2,6-isomer) in dic:hlorobenzene followed by distillation. The diisocyan-atcl-diphenylmethane was an isomeric mixture of 93.7% by weight of 4,4'-diisocyanato-diphenylmethane, 6.1% by wei.ght of 2,4'-diisocyanato-diphenylmethane and 0~2% by wei.ght of 2,2'-diisocyanato-diphenylmethane.
The sump product contained about 45 ppm (weight) of free TD]: and had a viscosity of 335 mPa.s at 25C and an iso-cyanate content of 28.4%.
Surnp product II:
The starting material used consisted of a mixture of 2.5parts by weight of TDI distillation residue and 5.5 parts by weight of a polyisocyanate consisting of 45.0% by weight of 4,4'-diisocyanato-diphenylmethane, 2.3% by we:ight of 2,4'-diisocyanatodiphenylmethane and about 50%
by weight of higher homologues of diisocyanatodiphenyl-methane containing more than 2 isocyanate groups per mo:Lecule.
.
Le A 28 829 10 . , .. ,.. , ..... ... .......... . . . , .. , .. ..... ~ . .. ....
f ~-` 212~1~5 .
The sump product obtained contained 5S ppm (weiyht) of ;
free TDI and had a viscosity of 4700 mPa.s at Z5C and an isocyanate content of 27.8%.
Preparation of polyurethane foams:
The so-called hand mixing process was employed for producing the PUR rigid foam in the following Examples.
A ~antity of about l kg was prepared in each case from the! polyol mixture without blowing agent and was tempered at 20-C in closed containers in a so-called air condition-ing cupboard. The test foams were prepared from about 300g of reaction mixture. For this purpose, the appropriate quantity of the polyol mixture was first weighed into a paper cup with metal base (diameter about 9 cm, height about 14 cm) and the blowing agent was added. Mixing was carried out with an electrically driven disc stirrer (about lO00 revs/min). The loss of blowing agent was de1:ermined by back weighing and replaced. The quantity of isocyanate required for the formulation was then added and the mixture was stirred for lO to 15 seconds.
After the components had been mixed, the reaction mixture was immediately poured into a box made of wrapping paper having a base of 20 x 20 cm2 and a height of 14 cm to produce a so-called test pack foam. The reaction times (e.g. gel time) were measured on the foam which was being produced. The gross density was determined on the finished foam.
Foam blocks measuring 24 cm x 24 cm x 8.0 cm were produced to test the properties of the foams. A laboratory book-binding press whose press plates (aluminium) had been tempered to 35-C by water flowing through them was used for this purpose. An aluminium frame which had the Le A 28 829 ll ... , . ' ~
2125155 :
internal dimensions 24 cm x 24 cm x 8.0 cm and had been preheated to 35~C was placed on the lower plate of the open press. A box made of wrapping paper and having the same external dimensions was placed in the frame and the reaction mixture was poured in. A sheet of wrapping paper was placed on the frame and the press was closed. The foam body was removed after about 30 minutes.
Le A 28 829 12 ....... . . ~
-- 2~2~1~5 : ~
Exam~le 1 ~
Pre!paration of a polyurethane foam expanded by means of ~;
monofluorotrichloromethane (R 11) 1.8 Parts by weight of water, 2.6 parts by weight of N,N-dimethyl-cyclohexylamine as reaction accelerator, 1.6 parts by weight of foam stabilizer Tegostab 8404 (Th.
Goldschmidt Company) and 38 parts by weight of blowing agent R 11 were added to 85 parts by weight of a polyether polyol prepared by the propoxylation of saccharose and ethylene glycol (molar ratio 2:1) with OH 460 and the components were mixed by stirring. This mixture was then stirred up with 135 parts by weight of sump product I. The initially brittle foam was tough after about l hour.
Foaming data: Stirring time 10 s Resting time 15 s Gel time 7S s free gross density 21 kg/m3 A sample in the form of a foam plate 80 mm in thickness and having a gross density of 45 kg/m3 was found to have undergone the following changes in dimension after 48 hours' storage at 70C (dimensional stability according to DIlt 18 164 Part 1):
Length: -0.14 %
Width: -0.54 %
Thickness: -1.99 %.
Le A 28 829 13 O~; ~ ~ ~ ,,, 212~
Example 2 Production of a polyurethane foam expanded by means of water/difluoromonochloromethane (R 22) The following polyol mixture was first prepared in a be;~ker: 40 Parts by weight of propoxylated glycerol with OH number 250, 30 parts by weight of propoxylated sacchar-ose/propylene glycol mixture with OH number 380 (viscosity at 25C: 13,000 mPa.s), 9.4 parts by weight of propoxyl-ated triethanolamine, OH number 150, 20.6 parts by weight of propoxylated triethanolamine, OH number 500, and 10 pa,rts by weight of propoxylated sorbitol, OH number 1390, containing 33% by weight of ethylene glycol.
3,5 Parts by weight of water, 2 parts by weight of foam s1:abilizer B 8443 (Th. Goldschmidt Company), 8 parts by weight of tris-chloropropyl-phosphate as flame retardant and 3.3 parts by weight of N,N-dimethylbenzylamine as r~eaction accelerator were added to this mixture. The mixture was stirred and 6 parts by weight of difluoro-mor.ochloromethane was added in the form of a gas. 100 Parts by weight of this polyol mixture were intimately ixed with 140 parts by weight of sump product I. The initially brittle foam became tough after about 1 hour.
~oaming data: Stirring time 10 s Resting time 17 s Gel time 68 s free gross density 34 kg/m3 ~
A sample of foam in the form of a plate having a thickness of 80 mm and a gross density of 45 kg/m3 was found to have undergone the following changes in dimensions after 48 hours' storage at 70C (dimensional stability according to Le A 28 829 14 ~2~
DIN 18 164 Part 1):
Length: +o.s %
Width: -0.3 %
Thickness: -0.68 %
The compressive strength (according to DIN 53 421) of another sample was:
parallel to the direction of foaming: 0.33 MPa perpendicular to the direction of foaming: 0.35 MPa.
Example 3 Preparation of a polyurethane foam expanded by means of water/pentane The polyol formulation was prepared according to Example 2 but without the difluoromonochloromethane as blowing agent.
100 Parts by weight of the polyol formulation were mixed with 157 parts by weight of sump product I to which 7 parts by weight of n-pentane had been added with vigorous -stirring. The foam produced was tough after about 2 hours.
Foaming data: Stirring time 10 s Resting time 21 s Gel time 79 s Free gross density 24 kg/m3.
A sample of foam in the form of a plate having a thickness of 80 mm and a gross density of 45 kg/m3 was found to have undergone the following linear changes in dimension after 48 hours' storage at 70C (dimensional stability according to DIN 18 164 Part 1):
Le A 28 829 15 21251~5 Length: -0.84 %
Width: -0.51 %
Thickness: -0.68 ~.
The compressive strength (according to DIN 53 421) of another sample was:
parallel to the direction of foaming: 0.10 MPa perpendicular to the direction of foaming: 0.28 MPa.
Example 4 Preparation of a foam expanded by means of CO2 The following polyol mixture was first prepared in a beaker: 50 parts by weight of propoxylated saccharose/p-ropylene glycol/ethylene glycol mixture, OH number 460 (viscosity at 25-C: 6000 mPa.s), 35 parts by weight of propoxylated saccharose/propylene glycol mixture, OH
number 380 (viscosity at 25-C: about 600 mPa.s) and 15 parts by weight of a phosphonic acid ester, OH number 450 (Desmophen 4090 N, Bayer AG). 2.45 Parts by weight of water, 1.5 parts by weight of foam stabiliæer SR 242 (Union Carbide Company) and 1.8 parts by weight of N,N-dimethyl-cyclohexylamine as reaction accelerator were added to this mixture. After the mixture had been homo-genised by stirring, 150 parts by weight of sump product I
were added and stirred in. The initially brittle foam became tough after about 2 hours.
25 Foaming data: Stirring time 15 s Resting time 25 s -~ -Gel time 56 s Free gross density 50 kg/m3 Le A 28_829 16 _ -~ 212515~
Determination of the dimensional stability according to DIN 18 159, Part l (48 hours' storage at lOO-C under a load o~ 0.02 N/mm2) indicated an average change in thickness of 1.4%.
Compressive strength according to DIN 53 421:
parallel to the direction of foaming 0.25 MPa, perpendicular to the direction of foaming 0.29 MPa.
Example 5 Preparation of a polyurethane foam expanded by means of The polyol mixture to be foamed was prepared as in Example 4.
oa Parts by weight of the polyol formulation were intensively stirred together with 150 parts by weight of sump product II to which 75 parts by weight of Desmodur(R) 44~10 (polyisocyanate of the diphenylmethane series, Bay~er AG) had been added. The initially brittle foam became tough after one hour.
Foa,ming data: Stirring time 15 s Resting time 27 s Gel time 60 s free gross density 50 kg/m3 The compressive strength (according to DIN 53 421) of another sample was:
parallel to the direction of foaming: 0.28 MPa perpendicular to the direction of foaming: 0.32 MPa.
Le A 28 829 17 - . 2~2~5 Exalm~le 6 Preparation of a polyurethane foam of building material Class B2 expanded by means of CO2 (fire characteristics acc:ording to DIN 4102) 20 Parts by weight of a polyester polyol prepared by the propoxylation of phthalic acid diethylene glycol mono-est:er, OH number 300, were mixed with 60 parts by weightof a bromine-containing polyether polyol (Ixol B251, Sol.vay) OH number 330, 10 parts by weight of a propylene oxi.de polyether based on glycerol, OH number 250, 10 parts by weight of a phosphonic acid ester, OH number 450 (De!smophen 4090 N, Bayer AG) and 35 parts by weight of a tris-halogenalkylphosphate, e.g. tris-chloroisopropyl-phosphate, as flame retardant.
To this mixture were added 6 parts by weight of water, 1.5 parts by weight of foam stabilizer B 8443 (Goldschmidt Company) and 1.6 parts by weight of N,N-dimethylbenzyl- ~
ami.ne as reaction accelerator. 100 Parts by weight of this -preparation were mixed with 132 parts by weight of sump .~
20 product I. The foam produced became tough after about 4 ~ ~.
hours. ~ ` ' Foa:ming data: Stirring time 15 s Resting time 30 s Gel time 100 s free gross density 32 kg/m3 A s.ample of foam in the form of a plate having a thickness of 80 mm and a gross density of 45 kg/m3 was found to have undlergone the following linear changes in dimension after 48 hours' storage at 70-C (dimensional stability according to DIN 18 164 Part 1):
Le A 28 829 18 21251~S
Length: 0.4 %
Width: -0.6 ~
Thickness: -0.2 %
The compressive strength (according to DIN 53 421) of another sample was:
parallel to the direction of foaming: 0.18 MPa perpendicular to the direction of foaming: 0.25 MPa.
The results of the test according to DIN 4102 Part 1 enabled the product to classified as building material ~ :~
cla:,s B2.
Max.imum height of flame:
Edge flaming:l40 mm Surface flaming: 130 mm 130 mm 140 mm 130 mm 140 mm ::
15 Example 7 ~
Preparation of a polyisocyanurate foam o~ building :~ :
mat~erial class B2 which had been expanded with R 11 The following polyhydroxyl compounds are mixed together wit:h stirring:
37.2 Parts by weight of a polyether polyol prepared by the propoxylation of a saccharose and propylene glycol mixture (molar ratio 5.7:1), OH number 470, 18.6 parts by weight of a polyester polyol based on phthalic acid and diethyl-ene glycol, OH number 300, 12.1 parts by weight of a polyester polyol based on phthalic acid and diethylene glycol, OH number 440, and 6.2 parts by weight of ethoxy-lated nonyl phenol, OH number 86.
Le A 28 829 19 2 12 ~
The mixture was then stirred together with 0.7 parts by weight of foam stabilizer B 8404 and 16.4 parts by weight of tris-chloropropylphosphate as flame retardant and 0.3 .
part:s by weight of water. 33 Parts by weight of blowing age~lt R 11 and 3.6 parts by weight of a 25% solution of potassium acetate in diethylene glycol as well as 0.4 parts by weight of N,N-dimethyl-cyclohexylamine as reaction accelerator were added to 100 parts by weight of this mixture. The mixture was stirred together with 200 par1s by weight of sump product II. The initially brittle foam became tough after about 2 hours.
Foaming data: Stirring time 15 s ~ ~5 Resting time 26 s Gel time 66 s :~
free gross density 36 kg/m3 A sample of foam in the form of a plate having a thickness of 80 mm and a gross density of 45 kg/m3 was found to have undergone the following linear changes in dimension after 48 hours' storage at 70-C (dimensional stability according to DIN 18 164 Part 1):
Length: -0.84 %
Width: -0.51 %
Thickness: -0.68 %.
The compressive strength of another sample (according to DIN 53 421) was:
parallel to the direction of foaming: 0.28 MPa perlpendicular to the direction of foaming: 0.30 MPa.
The results of the test according to DIN 4102 Part 1 ena~bled the products to be classified as building material class B2.
Le .!~ 28 829 20 ~ ;~
;, Maximum height of flame:
Edge flaming: 120 mm Surface flaming: 120 mm 120 mm 120 mm 130 mm 120 mm ¦ Le A 28 829 21 . . ,' ' ~
~oaming data: Stirring time 10 s Resting time 17 s Gel time 68 s free gross density 34 kg/m3 ~
A sample of foam in the form of a plate having a thickness of 80 mm and a gross density of 45 kg/m3 was found to have undergone the following changes in dimensions after 48 hours' storage at 70C (dimensional stability according to Le A 28 829 14 ~2~
DIN 18 164 Part 1):
Length: +o.s %
Width: -0.3 %
Thickness: -0.68 %
The compressive strength (according to DIN 53 421) of another sample was:
parallel to the direction of foaming: 0.33 MPa perpendicular to the direction of foaming: 0.35 MPa.
Example 3 Preparation of a polyurethane foam expanded by means of water/pentane The polyol formulation was prepared according to Example 2 but without the difluoromonochloromethane as blowing agent.
100 Parts by weight of the polyol formulation were mixed with 157 parts by weight of sump product I to which 7 parts by weight of n-pentane had been added with vigorous -stirring. The foam produced was tough after about 2 hours.
Foaming data: Stirring time 10 s Resting time 21 s Gel time 79 s Free gross density 24 kg/m3.
A sample of foam in the form of a plate having a thickness of 80 mm and a gross density of 45 kg/m3 was found to have undergone the following linear changes in dimension after 48 hours' storage at 70C (dimensional stability according to DIN 18 164 Part 1):
Le A 28 829 15 21251~5 Length: -0.84 %
Width: -0.51 %
Thickness: -0.68 ~.
The compressive strength (according to DIN 53 421) of another sample was:
parallel to the direction of foaming: 0.10 MPa perpendicular to the direction of foaming: 0.28 MPa.
Example 4 Preparation of a foam expanded by means of CO2 The following polyol mixture was first prepared in a beaker: 50 parts by weight of propoxylated saccharose/p-ropylene glycol/ethylene glycol mixture, OH number 460 (viscosity at 25-C: 6000 mPa.s), 35 parts by weight of propoxylated saccharose/propylene glycol mixture, OH
number 380 (viscosity at 25-C: about 600 mPa.s) and 15 parts by weight of a phosphonic acid ester, OH number 450 (Desmophen 4090 N, Bayer AG). 2.45 Parts by weight of water, 1.5 parts by weight of foam stabiliæer SR 242 (Union Carbide Company) and 1.8 parts by weight of N,N-dimethyl-cyclohexylamine as reaction accelerator were added to this mixture. After the mixture had been homo-genised by stirring, 150 parts by weight of sump product I
were added and stirred in. The initially brittle foam became tough after about 2 hours.
25 Foaming data: Stirring time 15 s Resting time 25 s -~ -Gel time 56 s Free gross density 50 kg/m3 Le A 28_829 16 _ -~ 212515~
Determination of the dimensional stability according to DIN 18 159, Part l (48 hours' storage at lOO-C under a load o~ 0.02 N/mm2) indicated an average change in thickness of 1.4%.
Compressive strength according to DIN 53 421:
parallel to the direction of foaming 0.25 MPa, perpendicular to the direction of foaming 0.29 MPa.
Example 5 Preparation of a polyurethane foam expanded by means of The polyol mixture to be foamed was prepared as in Example 4.
oa Parts by weight of the polyol formulation were intensively stirred together with 150 parts by weight of sump product II to which 75 parts by weight of Desmodur(R) 44~10 (polyisocyanate of the diphenylmethane series, Bay~er AG) had been added. The initially brittle foam became tough after one hour.
Foa,ming data: Stirring time 15 s Resting time 27 s Gel time 60 s free gross density 50 kg/m3 The compressive strength (according to DIN 53 421) of another sample was:
parallel to the direction of foaming: 0.28 MPa perpendicular to the direction of foaming: 0.32 MPa.
Le A 28 829 17 - . 2~2~5 Exalm~le 6 Preparation of a polyurethane foam of building material Class B2 expanded by means of CO2 (fire characteristics acc:ording to DIN 4102) 20 Parts by weight of a polyester polyol prepared by the propoxylation of phthalic acid diethylene glycol mono-est:er, OH number 300, were mixed with 60 parts by weightof a bromine-containing polyether polyol (Ixol B251, Sol.vay) OH number 330, 10 parts by weight of a propylene oxi.de polyether based on glycerol, OH number 250, 10 parts by weight of a phosphonic acid ester, OH number 450 (De!smophen 4090 N, Bayer AG) and 35 parts by weight of a tris-halogenalkylphosphate, e.g. tris-chloroisopropyl-phosphate, as flame retardant.
To this mixture were added 6 parts by weight of water, 1.5 parts by weight of foam stabilizer B 8443 (Goldschmidt Company) and 1.6 parts by weight of N,N-dimethylbenzyl- ~
ami.ne as reaction accelerator. 100 Parts by weight of this -preparation were mixed with 132 parts by weight of sump .~
20 product I. The foam produced became tough after about 4 ~ ~.
hours. ~ ` ' Foa:ming data: Stirring time 15 s Resting time 30 s Gel time 100 s free gross density 32 kg/m3 A s.ample of foam in the form of a plate having a thickness of 80 mm and a gross density of 45 kg/m3 was found to have undlergone the following linear changes in dimension after 48 hours' storage at 70-C (dimensional stability according to DIN 18 164 Part 1):
Le A 28 829 18 21251~S
Length: 0.4 %
Width: -0.6 ~
Thickness: -0.2 %
The compressive strength (according to DIN 53 421) of another sample was:
parallel to the direction of foaming: 0.18 MPa perpendicular to the direction of foaming: 0.25 MPa.
The results of the test according to DIN 4102 Part 1 enabled the product to classified as building material ~ :~
cla:,s B2.
Max.imum height of flame:
Edge flaming:l40 mm Surface flaming: 130 mm 130 mm 140 mm 130 mm 140 mm ::
15 Example 7 ~
Preparation of a polyisocyanurate foam o~ building :~ :
mat~erial class B2 which had been expanded with R 11 The following polyhydroxyl compounds are mixed together wit:h stirring:
37.2 Parts by weight of a polyether polyol prepared by the propoxylation of a saccharose and propylene glycol mixture (molar ratio 5.7:1), OH number 470, 18.6 parts by weight of a polyester polyol based on phthalic acid and diethyl-ene glycol, OH number 300, 12.1 parts by weight of a polyester polyol based on phthalic acid and diethylene glycol, OH number 440, and 6.2 parts by weight of ethoxy-lated nonyl phenol, OH number 86.
Le A 28 829 19 2 12 ~
The mixture was then stirred together with 0.7 parts by weight of foam stabilizer B 8404 and 16.4 parts by weight of tris-chloropropylphosphate as flame retardant and 0.3 .
part:s by weight of water. 33 Parts by weight of blowing age~lt R 11 and 3.6 parts by weight of a 25% solution of potassium acetate in diethylene glycol as well as 0.4 parts by weight of N,N-dimethyl-cyclohexylamine as reaction accelerator were added to 100 parts by weight of this mixture. The mixture was stirred together with 200 par1s by weight of sump product II. The initially brittle foam became tough after about 2 hours.
Foaming data: Stirring time 15 s ~ ~5 Resting time 26 s Gel time 66 s :~
free gross density 36 kg/m3 A sample of foam in the form of a plate having a thickness of 80 mm and a gross density of 45 kg/m3 was found to have undergone the following linear changes in dimension after 48 hours' storage at 70-C (dimensional stability according to DIN 18 164 Part 1):
Length: -0.84 %
Width: -0.51 %
Thickness: -0.68 %.
The compressive strength of another sample (according to DIN 53 421) was:
parallel to the direction of foaming: 0.28 MPa perlpendicular to the direction of foaming: 0.30 MPa.
The results of the test according to DIN 4102 Part 1 ena~bled the products to be classified as building material class B2.
Le .!~ 28 829 20 ~ ;~
;, Maximum height of flame:
Edge flaming: 120 mm Surface flaming: 120 mm 120 mm 120 mm 130 mm 120 mm ¦ Le A 28 829 21 . . ,' ' ~
Claims (4)
1. A process for the production of rigid foams containing urethane groups and optionally isocyanu-rate groups by the reaction of a) polyisocyanates with b) compounds in the molecular weight range of from 400 to 10,000 having at least two isocyanate reactive hydrogen atoms t in the presence of c) water and/or readily volatile organic substances as blowing agents and optionally in the presence of d) compounds in the molecular weight range of from 32 to 399 having at least two isocyanate reactive hydrogen atoms, and e) auxiliary agents and additives known per se, characterised in that the polyisocyanates a) used consist of an isocyanate group-containing sump product having a tolylene diisocyanate content of less than 5 % b.w., preferably less than 1 % b.w., more preferably less than 200 ppm (weight), obtainable from A) distillation residues of tolylene diisocyanate production by mixing the distillation residues A) with B) polyisocyanates or polyisocyanate mixtures of the diphenylmethane series optionally modified with urethane and/or allophanate groups and having an isocyanate content of at least 15% by weight and working up the mixture by distillation, the mixture being heated to temperatures of from 190 to 250°C
before or during the distillative working up, whereby the tolylene diisocyanate which is reversibly bound in the distillation residue A) undergoes substantial substitution by polyisocyan-ate B).
before or during the distillative working up, whereby the tolylene diisocyanate which is reversibly bound in the distillation residue A) undergoes substantial substitution by polyisocyan-ate B).
2. A process according to Claim 1, characterised in that component B) consists of 4,4'-isocyanato-diphenylmethane, its commercial mixtures with 2,4'-and optionally 2,2'-diisocyanatodiphenylmethane or mixtures of these diisocyanatodiphenylmethane isomers with up to 65% by weight, based on the mixture, of their higher homologues containing more than 2 isocyanate groups per molecule.
3. A process according to Claims 1 and 2, character-ised in that sump products containing isocyanate groups are used, which have been mixed with from 20 to 80% by weight, preferably from 40 to 60% by weight, of polyisocyanates of the diphenylmethane series.
4. A process according to Claims 1 to 3, characterised in that the polyisocyanates of the diphenylmethane series added are mixtures of the diisocyanato-diphenylmethane isomers with up to 65% by weight (based on the mixture) of their higher homologues having more than 2 isocyanate groups per molecule.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4200325A DE4200325A1 (en) | 1992-01-09 | 1992-01-09 | METHOD FOR PRODUCING HARD URETHANOUS GROUPS |
| DEP4200325.3 | 1992-01-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2125155A1 true CA2125155A1 (en) | 1993-07-22 |
Family
ID=6449240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002125155A Abandoned CA2125155A1 (en) | 1992-01-09 | 1992-12-28 | Process for the production of rigid foams containing urethane groups |
Country Status (5)
| Country | Link |
|---|---|
| AU (1) | AU3258493A (en) |
| CA (1) | CA2125155A1 (en) |
| DE (1) | DE4200325A1 (en) |
| WO (1) | WO1993014139A1 (en) |
| ZA (1) | ZA93124B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1756224B1 (en) | 2004-05-28 | 2007-10-17 | Albemarle Corporation | Flame retardant polyurethanes and additives therefor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3455836A (en) * | 1966-10-10 | 1969-07-15 | Allied Chem | Polyisocyanate compositions |
| DE2123183A1 (en) * | 1971-05-11 | 1972-12-14 | ||
| US3887502A (en) * | 1972-05-12 | 1975-06-03 | Olin Corp | Preparation of rigid polyurethane foam having improved aging properties |
| GB1434917A (en) * | 1972-06-02 | 1976-05-12 | Ici Ltd | Isocyanates |
-
1992
- 1992-01-09 DE DE4200325A patent/DE4200325A1/en not_active Withdrawn
- 1992-12-28 CA CA002125155A patent/CA2125155A1/en not_active Abandoned
- 1992-12-28 AU AU32584/93A patent/AU3258493A/en not_active Abandoned
- 1992-12-28 WO PCT/EP1992/003004 patent/WO1993014139A1/en active Application Filing
-
1993
- 1993-01-08 ZA ZA93124A patent/ZA93124B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU3258493A (en) | 1993-08-03 |
| ZA93124B (en) | 1993-08-09 |
| WO1993014139A1 (en) | 1993-07-22 |
| DE4200325A1 (en) | 1993-07-15 |
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