CA2113433A1 - Polyisocyanate compositions - Google Patents
Polyisocyanate compositionsInfo
- Publication number
- CA2113433A1 CA2113433A1 CA002113433A CA2113433A CA2113433A1 CA 2113433 A1 CA2113433 A1 CA 2113433A1 CA 002113433 A CA002113433 A CA 002113433A CA 2113433 A CA2113433 A CA 2113433A CA 2113433 A1 CA2113433 A1 CA 2113433A1
- Authority
- CA
- Canada
- Prior art keywords
- polyisocyanate
- isocyanate
- uretonimine
- composition according
- modified
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides organic polyisocyanate compositions comprising a polyisocyanate component and a non-ionic surface active agent devoid of isocyanate-reactive groups characterised in that the polyisocyanate component comprises an isocyanate-containing reaction product of a uretonimine-modified polyisocyanate and a polyol having a molecular weight of from 500 to 10,000. The invention further provides aqueous emulsions derived from the polyisocyanate compositions, a method of their use for binding polyurethane foam scrap and foam composites prepared by the method.
Description
- 1 - 211~ l33 POLYISOCYANATE COMPOSITIONS
This invention relates to polyisocyanate compositions and more particularly to water-emulsifiable polyisocyanate compositions, to methods for their preparation, to the derived aqueous emulsions and to the use of said emulsions as binders.
Organic polyisocyanate compositions which are emulsifiable in water are already known as is the use of the derived aqueous emulsions as binders and adhesives. Thus, in United Kingdom Patent Specifications Nos. 1,444,933 and 1,523,601, there are described emulsifiable polyisocyanate compositions comprising an organic isocyanate and a non-ionic surface active agen~ free of hydroxy, amino and carboxylic acid qroups. Isocyanates whic~ may be present in said compositions include aliphatic, cycloaliphatic and, especially, aromatic polyisocyanates and also isocyanate-~nded prepolymers made by reaction of an excess of a polyisocyanate with a polyester or polyether polyol, a monomeric polyol or castor oil. The derived aqueous emulsions may be applied to wood chips and other ligno-cellulosic materials to produce particle boards and similar composite articles.
In order for the aqueous emulsion. to have commercial utility, it is desirable that they s~ould be stable for a period of several hours and, preferably, for several days.
SUBSTITIJTE SHEET
This invention relates to polyisocyanate compositions and more particularly to water-emulsifiable polyisocyanate compositions, to methods for their preparation, to the derived aqueous emulsions and to the use of said emulsions as binders.
Organic polyisocyanate compositions which are emulsifiable in water are already known as is the use of the derived aqueous emulsions as binders and adhesives. Thus, in United Kingdom Patent Specifications Nos. 1,444,933 and 1,523,601, there are described emulsifiable polyisocyanate compositions comprising an organic isocyanate and a non-ionic surface active agen~ free of hydroxy, amino and carboxylic acid qroups. Isocyanates whic~ may be present in said compositions include aliphatic, cycloaliphatic and, especially, aromatic polyisocyanates and also isocyanate-~nded prepolymers made by reaction of an excess of a polyisocyanate with a polyester or polyether polyol, a monomeric polyol or castor oil. The derived aqueous emulsions may be applied to wood chips and other ligno-cellulosic materials to produce particle boards and similar composite articles.
In order for the aqueous emulsion. to have commercial utility, it is desirable that they s~ould be stable for a period of several hours and, preferably, for several days.
SUBSTITIJTE SHEET
2113`13 3 2 -Unfortunately, many of the know~ emulsifiable polyisocyanates have not been entirely satisfactory in this respect, the derived emulsions showing undesirable phase separation and/or reduction in isocyanate value after a relatively short period of time.
It has now been found that agueous emulsions having improved stability may be obtained from emulsifiable polyisocyanates derived from prepolymers of uretonimine-modi~ied polyisocyanates.
Thus, according to the invention, there is provided an organic polyisocyanate composition comprising a polyisocya~ate component and a non-ionic surface active agent devoid of isocyanate-reactive groups characterised in that the polyisocyan~te component comprises an isocyanate-contAining reaction product of a uretonimine-modified polyisocyanate and a polyol having a molecular weight of from S00 to lO,000.
The isocyanate-containing reaction product (a prepolymer containing urethane and uretonimine groups) may be obtained by reacting a polyol with a stoichiometric ex~ess of a uretonimine-modified polyisocyanate under conditions that ha~e been fully described in the prior art for the preparation of urethane prepolymers. Reaction temperatures of from about 40 to about 90-C are qenerally suitable, the excess of uretonimine-modified polyisocyanate being such as to give a reaction product having an isocyanate (NCO) content in the SUBSTITUTE SHE~, WO 93~03082 2113 4 3 3 PCT/GB92/01452 range from about 2 to about 25 ~ on a weight basis, preferably from about ll to about l5 %
Polyols which may be used in ma~ing the isocyanate-containing prepolymer preferably have hydroxyl functionalities of from 2 to 4, diols and triols and mixtures thereof being preferred.
Particularly suitable polyols include polyether polyols, for example polyoxy-propylene and poly(oxypropylene-oxyethylene) diols and triols and, especially hydroxyl-containing fatty acid esters such as castor oil and hydrogenated castor oil. Other polyols which may be used include hydroxyl-terminated polyesters, polyesteramides, polythioethers, polycarbcnates, ; polyacetals, polyolefins and polysiloxanes. Mixtur~s of polyols may be used, ~or example mixtures of polyoxy-propylene polyols and castor oil.
Uretoni~ine-modified polyisocyanates which may be used in making the isocyanate-containing prepolymer, and methods for their prepara~ion, have been fully de~cribed in the prior art.
In general, uretonimine-modified polyisocyanates are obtained by contacting an organic polyisocyanat~ with a carbodiimid-isation catalyst (commonly a phosphorus compou~d) to form acarbodiimide-modified polyisocyanate which reacts with unreacted isocyanate groups forming a uretonimine-modified polyisocyanate. Suitable phosphorus-co~taining catalysts include alkyl esters of phosphoric, phosphonic, phosphinic, phosphorous and phosphinous acids and the corresponding amides, SUBST~TUTE~ SHEET
2113~i33 4 _ phosphine oxides and the phospholidines and phospholenes described in United Kingdom Patent Specification No. 1,476,088.
In a typical procedure, the organic polyisocyanate is heated with an effective amount of a carbodiimidisation catalyst so as to convert from 5 to 40 S of the isocyanate groups to carbodiimide groups, the reaction mixture then being cooled, the catalyst being deactivated if desired or necessary and reaction between carbodiimide and isocy~nate groups beinq allowed to take place to form the uretonimine derivative, thereby res~lting in 7.5 ~ to 60 %, and preferably 10 % to 40 %
conversion of initially present isocyanate groups into uretonimine-modified form.
Organic polyisocyanatas from which the uretonimine-modified polyisocyanates may be prepared include aliphatic, cyclo-aliphatic and araliph~tic polyisocyanates, for example hexa-~; methylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and m-~nd p- tetramethylxylene diisocyanatas. The preferred poly~socyanates, however, are the aromatic polyisocyanates, for axample phenylene diisocyanates, 2,4-and 2,6-tolylene diisooyanates, 1,5-napthylene diisocyanate and especially the available isomers of diphenylmethane diisocyanate (MDI), that is to say 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and mixtures thereof. Other suitable polyisocyanates include the mixtures of diphenylmethane diisocyanates with oligomeric tri- and hig~er ~ polyisocyanates known in the art as crude or polymeric MDI.
:
~ ~ SUBSTITUTE SHEET
; ~ ' W093/0308~ 2113 !1 3 ~ PCT/GB92/01452 If desired, the polyisocyanate component may contain other isocyanate species, for example any of the organic polyisocyanates mentioned above, in addition to the prepolymer derived from the uretonimine-modified polyisocyanate. One preferred polyisocyanate component comprises a mixture of polymeric MDI and a prepolymer obtained by reacting uretonimine-modified diphenylmethane diisocyanate with a polyoxypropylene polyol and/or castor oil.
The non-ionic surface active agent devoid of isocyanate-reactive groups present in the compositions of the invention may be any of such agents described in the prior art. In particular, such agents include polyoxyalkylene, especially polyoxyethylene, compounds containing no free hydroxy, amino, carboxy or other isocyanate-reactive groups. These include, for example, condensates of alkylphenyls, long chain alcohols and amides with alkylene oxides, especially ethylene oxide, the terminal ~ydroxy group being etherified or esterified.
Examp~es of such surface active agents have been described in the aforementioned United Xingdom Specifications 1,444,933 and 1,523,601 and in EP-A-0 019 844 and EP-A-0 095 594.
Of particular value are the reaction products of diisocyanates and higher functionality polyisocyanates with monoalkyl ethers of polyethylene glycols as described in United Kingdom Patent Specification No. 1,417,618. These particular surface active agents or emulsifying agents have the formula RO(CH2CH2O)nCONHX
SUBSTITUTE SHE~T
2113~33 wherein R is an alkyl group of from 1 to 4 carbon atoms, n is an integer such that the compound contains an average of at least 5 oxyethylene groups and X is t~e residue of a di- or polyisocyanate and contains at least one free isocyanate group.
Examples of R include ethyl, propyl, butyl, and preferably methyl. It is preferred that n represents an average of from 5 to 120, and especially from 10 to 20.
The group X is the residue which would remain after one isocyanate group has been removed. The group X may be the residue of any diisocyanate or higher polyisocyanate and for example if the diisocyanate is a tolylene diisocyanate, the residue X will be Isocyanates from which the group X can be derived include the di- and polyisocyanates listed above, the uretonimine-modified polyisocyanates made therefrom and the isocyanate-containing prepolymers derived from the uretonimine-modified polyisocyanates. Such surface active urethanes may be ~anufactured by reacting an alcohol of the formula RO(CH2CH2O)nH
wherein R and n have the same meanin~ as for the above described surface active or emulsifying agents, with an isocyanate having at least two isocyanate groups, there being , ~ ~
~ used at least one molar proportion of isocyanate for each molar SUE~STITUTE SH~El 211~ i3`3 proportion of the alcohol. Preferably an excess of the isocyanate is used.
~he reaction may be carried out by adding the alcohol to the isocyanate and allowing the reaction to proceed, preferably by heating thé reactlon mixture at a temperature of 50-150-C.
Alternatively the reaction can be carried out at lower temperatures e.g. 2S-C in the presence of a small a~ount of catalyst e.g. triethylenediamine.
In order to obtain emulsifiable polyisocyanates according to the present invention, the above type of surface active aqent may be prepared in situ in the polyisocyanate compon~nt by reacting a ~mall amount of the polyethylenoxy alcohol RO ~CH2CH20) nH -wlth a l~rge excess of that component.
A further type of surface active agent which may be utilised is that described in United Xingdom Patent Specification No.
1,417,276 which has the general formula COO(CH2CH2O)mR
R-X-NHCOCN
COO (CH2CH20) nR
~ ~ .
~ wherein X îs the residue of an organic isocyanate, R1 is an ,.,.~, i ~ -l alkyl group of from 1 to 4 carbon atoms, n and m are integers such that m+n is at least 10 and R, which is only present when X represents the residue of a diisocyanate or a higher ::
functionallty polyisocyanate, is an isocyanate group or a group ` of the formuIa SUBSTITUTE SHEET
W093/03082 PCT/GBg2/014~2 2113~13~ 8 -~ COO (CH2CH20) mR
-NHCOCH
~ COO tCH2CH20) nRl Rl is preferably methyl and the sum of m and n is preferably between 20 and 80.
X may for example be the residue of any of the isocyanates (including prepolymers) listed earlier in this specification.
These surface active agents or emulsifiers may be made by reaction of an isocyanate with a bis(alkoxy polyethylenoxy) ester of malonic acid, and ~ay if ~esired be prepared in situ in the polyisocyanate component.
The amount of the .non-ionic, surface-active agent in tha polyisocyanate composition according to the present invention may range from 0Ol to 15 and preferably from 0.5 to 10 ~ by weight calculated on the whole composition.
From the polyisocyanate co~positions according to the present invention aqueous ~mulsions can be made, said emulsions exhibiting an improved stability and pot-life. The emulsions may comprise 99 to 25 parts by weight of water and 1 to 75 parts by weight of the polyisocyanate composition according to the present invention. Preferably they comprise 70 to 50 parts by weiqht of water and 30 to 50 parts by weight of the polyisocyanate composition. Such emulsions are made by combining the polyisocyanate composition and the water while and/or followed by thoroughly mixing at ambient temperature.
:
: SUBSTITUTE SHEET
:~
W093/03082 2 1 1 3 ~ ~ ~ PCT/GB92/01452 The emulsions may furt~er contain additives such as pigments, fillers, antioxidants, resins and plasticisers.
The emulsions are useful as adhesives, coatings, sizing-agents of paper and particularly as binders of lignocellulosic materials like woodchips and straw, in view of their excellent stability.
When the aqueous emulsions derived from the compositions of the invention are used as binders, known techniques may be employed, for example the technigues described in the afore-~entioned United Xingdom Specifications 1,444,933 and 1,523,601, EP-A-0 019 844 and E2-A-0 095 594.
The aqueous emulsions of the invention are also of particular value as binders for polyurethane foam scrap, especially flexible foam scrap which can be reconstituted for use as resilient backing for woven or tufted carpets. In a typical procedure, pieces of scrap foam are impregnated with the aqueous emulsion and the treated foam is compressed in a mould and injected with steam to promote cure.
The invention is il~ustrated but not limited by the following Examples in which all parts and percentages are by weight.
Exam~le 1 A prepolymer having an NCO content of 13.7 % was prepared by reacting 62 parts of an isocyanate with a ure~onimine content SUBSTITUTE SHEET
W093/03082 PCT/GB92/014~2 2113'13~ - lO-of 16.4 ~ with 35 parts of castor oil and 3 parts of the monomethyl ether of polyethylene glycol having a molecular weight of 750.
A 30 % aqueous emulsion was prepared. The initial NCO content was measured and the change in NCO content then monitored during subsequent storage of the emulsion :
NCO content Initial 4~1 %
15 mins 3.6 %
45 mins 3.2 % Reduction of NCO content 100 mins 3.2 % at 180 minutes - 27 % (interpola~ion) 300 mins 2.6 %
Exam~le 2 A pxepolymer having an NCO content of 13.7 ~ W~5 prepared as described in Example 1. A 47 % emulsion of the prepolymer in water, containing 5 % of butyl benzyl phthalate, was prepared.
Initial and subsequent NCO contents were found to be as follows :
~CO conten~
Initial 6.1 %
6~ mins 6.1 ~ Reduction of NCO content 120 mins 5.1 % at 180 ~inutes = 15 % (extrapolation) 2113~33 Emulsion stability was better than in Example 1.
Exam~le 3 A prepolymer having an NC0 content of 13.0 % was prepared by reacting 54 pts of an i~ocyanate having a uretonimine content of 16.4 % with 24.5 pts of castor oil, 8.5 pts of poly bdR-45HT, (a hydroxyl terminated polybutadiene resin with a molecular weight of 2500), 10 pt- of butyl benzyl phthalate and 3 pts of the monomethyl ether of polyethylene glycol having a ~: mo}ecular weight of 750.
A 40 % aqueous emulsion was prepared. Initial and ~ubseguent :NQ0 contents were foùnd to be as follows : _ NC0 content.
Initial 5.2 %
30 mins 4.8 % Reduction of NC0 content 200 mins 4.2 S at 180 minutes - 21 % (interpolation) 1440 ~ins 1.0 ~: ~
:
ExamDle 4 A prepolymer having an NC0 content of 12.8 % was prepared by reacting 54 pts of an isocyanate haYing a uretonimine content of 16.4 % with 24.5 pts of castor oil, 8.5 pts of ~erathane 2000 (a polytetramethylene ether glycol of molecular weight 20Q0 : Terathane is a Registered Trade Mark), 10 pts of butyl benzyl phthalate and 3.0 pts of the monomethyl ether of polgethylene glycol having a molecular weight of 750.
-, , ~ ~.
SUBSTITUTE SHEET
A 40 % aqueous emulsion was prepared. Initial and subsequent NC0 contents were found to be as follows :
NCO content Initial 5.14 %
25 mins 4.6 % Reduction of NC0 content 90 mins 4.2 ~ at 180 minutes = 32 ~ (extrapolation) 160 mins ~.6 %
* product precipitating and foaming Comparison Example 5 A prepolymer having an NC0 content of 17.6 % was prepared by reacting 65.5 pts of~Suprasec 1042 (a commercially available emulsifiable polyisocyanate containing no uretonimine-mo~ified polyisocyanate components) with 34.5 pts of a 2000 ~olecular weight polypropylene glycol diol. (5uprasec is a Reqistered Trademar~).
A 30 % aqueous emulsion was prepared. The initial and subsequent NC0 contents were found to be as follows :
O con~ent Initial 5.3 %
lO mins 4.8 % Reduction of NC0 content 30 mins 3.9 % at 180 minutes = 93 %
45 mins 2.9 %
180 mins 0.35 SUBSTITUTE S~4EET
Comparison of the reduction in NCo content on storage of a~
emulsion derived from a non-uretonimine modified emulsifiable polyisocyanate (Example 5) with those observed for emulsions prepared from polyisocyanates according to the invention shows a substantial improvement in pot-life for the invention compositions.
Aqueous emulsions derived from the invention compositions, when used as binders for foam scrap, yield foam composites having good properties, as shown in Table I. Properties of a foa~
composite derived from a standard toluene diisocyanate (TDI) prepolymer (TDI, 3000 molecular weight polypropylene glycol, triol and mineral oil) are reported in Table I for comparison purposes.
~ ~ SUBSTlTUTE SHEET
:
WO 93/03082 PCI`/GB92/014~2 2 1 1 3 ~ 3 ) 14 -Table I - ProPerties of Foam Composites.
'il Oerived frcm Ellulsion ¦Deri~d fran Em~lsir~ ¦ S~ardard fo~
of Ex~nple 2 ¦of E~nple 3 ¦ derived fro~ ~DI
~ight X ai~der Le~el 4 5 6 I S 6 l 6.5 O ~it~ U U 1 80 er6ile strength (Il) ¦~ 6.9 5.3 1 ~.4 10.2 ~ 10.9 ~befor~t~on) 1~ ', j~ I
~or~ o~ to9 1~9 lt3 j 14~ 150 ~ 134 ~J~2) . I ~
t~ ) Att~r D~alic lo~ding ~_ ~2 116 1 111 _ 120 1 10t X ~o~s ~ _22 ,~ '~ 9 20.4 1 ;~0.4 _. ~ ~
Co~arisrn Orl9irel ~o) ~.9 ~ .1 6.3 6.0 ¦ 6.5 /~f~er ~k, loadinq (~ 6.~ 6.5 ~.6 6 1 5.9 6.2 ~hickness ~ X~ _~ s.r O.z 6.1 S~ 6.0 ~S211t.2) ._ I _ , _ - SVBSTITUTE S~EET
It has now been found that agueous emulsions having improved stability may be obtained from emulsifiable polyisocyanates derived from prepolymers of uretonimine-modi~ied polyisocyanates.
Thus, according to the invention, there is provided an organic polyisocyanate composition comprising a polyisocya~ate component and a non-ionic surface active agent devoid of isocyanate-reactive groups characterised in that the polyisocyan~te component comprises an isocyanate-contAining reaction product of a uretonimine-modified polyisocyanate and a polyol having a molecular weight of from S00 to lO,000.
The isocyanate-containing reaction product (a prepolymer containing urethane and uretonimine groups) may be obtained by reacting a polyol with a stoichiometric ex~ess of a uretonimine-modified polyisocyanate under conditions that ha~e been fully described in the prior art for the preparation of urethane prepolymers. Reaction temperatures of from about 40 to about 90-C are qenerally suitable, the excess of uretonimine-modified polyisocyanate being such as to give a reaction product having an isocyanate (NCO) content in the SUBSTITUTE SHE~, WO 93~03082 2113 4 3 3 PCT/GB92/01452 range from about 2 to about 25 ~ on a weight basis, preferably from about ll to about l5 %
Polyols which may be used in ma~ing the isocyanate-containing prepolymer preferably have hydroxyl functionalities of from 2 to 4, diols and triols and mixtures thereof being preferred.
Particularly suitable polyols include polyether polyols, for example polyoxy-propylene and poly(oxypropylene-oxyethylene) diols and triols and, especially hydroxyl-containing fatty acid esters such as castor oil and hydrogenated castor oil. Other polyols which may be used include hydroxyl-terminated polyesters, polyesteramides, polythioethers, polycarbcnates, ; polyacetals, polyolefins and polysiloxanes. Mixtur~s of polyols may be used, ~or example mixtures of polyoxy-propylene polyols and castor oil.
Uretoni~ine-modified polyisocyanates which may be used in making the isocyanate-containing prepolymer, and methods for their prepara~ion, have been fully de~cribed in the prior art.
In general, uretonimine-modified polyisocyanates are obtained by contacting an organic polyisocyanat~ with a carbodiimid-isation catalyst (commonly a phosphorus compou~d) to form acarbodiimide-modified polyisocyanate which reacts with unreacted isocyanate groups forming a uretonimine-modified polyisocyanate. Suitable phosphorus-co~taining catalysts include alkyl esters of phosphoric, phosphonic, phosphinic, phosphorous and phosphinous acids and the corresponding amides, SUBST~TUTE~ SHEET
2113~i33 4 _ phosphine oxides and the phospholidines and phospholenes described in United Kingdom Patent Specification No. 1,476,088.
In a typical procedure, the organic polyisocyanate is heated with an effective amount of a carbodiimidisation catalyst so as to convert from 5 to 40 S of the isocyanate groups to carbodiimide groups, the reaction mixture then being cooled, the catalyst being deactivated if desired or necessary and reaction between carbodiimide and isocy~nate groups beinq allowed to take place to form the uretonimine derivative, thereby res~lting in 7.5 ~ to 60 %, and preferably 10 % to 40 %
conversion of initially present isocyanate groups into uretonimine-modified form.
Organic polyisocyanatas from which the uretonimine-modified polyisocyanates may be prepared include aliphatic, cyclo-aliphatic and araliph~tic polyisocyanates, for example hexa-~; methylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and m-~nd p- tetramethylxylene diisocyanatas. The preferred poly~socyanates, however, are the aromatic polyisocyanates, for axample phenylene diisocyanates, 2,4-and 2,6-tolylene diisooyanates, 1,5-napthylene diisocyanate and especially the available isomers of diphenylmethane diisocyanate (MDI), that is to say 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and mixtures thereof. Other suitable polyisocyanates include the mixtures of diphenylmethane diisocyanates with oligomeric tri- and hig~er ~ polyisocyanates known in the art as crude or polymeric MDI.
:
~ ~ SUBSTITUTE SHEET
; ~ ' W093/0308~ 2113 !1 3 ~ PCT/GB92/01452 If desired, the polyisocyanate component may contain other isocyanate species, for example any of the organic polyisocyanates mentioned above, in addition to the prepolymer derived from the uretonimine-modified polyisocyanate. One preferred polyisocyanate component comprises a mixture of polymeric MDI and a prepolymer obtained by reacting uretonimine-modified diphenylmethane diisocyanate with a polyoxypropylene polyol and/or castor oil.
The non-ionic surface active agent devoid of isocyanate-reactive groups present in the compositions of the invention may be any of such agents described in the prior art. In particular, such agents include polyoxyalkylene, especially polyoxyethylene, compounds containing no free hydroxy, amino, carboxy or other isocyanate-reactive groups. These include, for example, condensates of alkylphenyls, long chain alcohols and amides with alkylene oxides, especially ethylene oxide, the terminal ~ydroxy group being etherified or esterified.
Examp~es of such surface active agents have been described in the aforementioned United Xingdom Specifications 1,444,933 and 1,523,601 and in EP-A-0 019 844 and EP-A-0 095 594.
Of particular value are the reaction products of diisocyanates and higher functionality polyisocyanates with monoalkyl ethers of polyethylene glycols as described in United Kingdom Patent Specification No. 1,417,618. These particular surface active agents or emulsifying agents have the formula RO(CH2CH2O)nCONHX
SUBSTITUTE SHE~T
2113~33 wherein R is an alkyl group of from 1 to 4 carbon atoms, n is an integer such that the compound contains an average of at least 5 oxyethylene groups and X is t~e residue of a di- or polyisocyanate and contains at least one free isocyanate group.
Examples of R include ethyl, propyl, butyl, and preferably methyl. It is preferred that n represents an average of from 5 to 120, and especially from 10 to 20.
The group X is the residue which would remain after one isocyanate group has been removed. The group X may be the residue of any diisocyanate or higher polyisocyanate and for example if the diisocyanate is a tolylene diisocyanate, the residue X will be Isocyanates from which the group X can be derived include the di- and polyisocyanates listed above, the uretonimine-modified polyisocyanates made therefrom and the isocyanate-containing prepolymers derived from the uretonimine-modified polyisocyanates. Such surface active urethanes may be ~anufactured by reacting an alcohol of the formula RO(CH2CH2O)nH
wherein R and n have the same meanin~ as for the above described surface active or emulsifying agents, with an isocyanate having at least two isocyanate groups, there being , ~ ~
~ used at least one molar proportion of isocyanate for each molar SUE~STITUTE SH~El 211~ i3`3 proportion of the alcohol. Preferably an excess of the isocyanate is used.
~he reaction may be carried out by adding the alcohol to the isocyanate and allowing the reaction to proceed, preferably by heating thé reactlon mixture at a temperature of 50-150-C.
Alternatively the reaction can be carried out at lower temperatures e.g. 2S-C in the presence of a small a~ount of catalyst e.g. triethylenediamine.
In order to obtain emulsifiable polyisocyanates according to the present invention, the above type of surface active aqent may be prepared in situ in the polyisocyanate compon~nt by reacting a ~mall amount of the polyethylenoxy alcohol RO ~CH2CH20) nH -wlth a l~rge excess of that component.
A further type of surface active agent which may be utilised is that described in United Xingdom Patent Specification No.
1,417,276 which has the general formula COO(CH2CH2O)mR
R-X-NHCOCN
COO (CH2CH20) nR
~ ~ .
~ wherein X îs the residue of an organic isocyanate, R1 is an ,.,.~, i ~ -l alkyl group of from 1 to 4 carbon atoms, n and m are integers such that m+n is at least 10 and R, which is only present when X represents the residue of a diisocyanate or a higher ::
functionallty polyisocyanate, is an isocyanate group or a group ` of the formuIa SUBSTITUTE SHEET
W093/03082 PCT/GBg2/014~2 2113~13~ 8 -~ COO (CH2CH20) mR
-NHCOCH
~ COO tCH2CH20) nRl Rl is preferably methyl and the sum of m and n is preferably between 20 and 80.
X may for example be the residue of any of the isocyanates (including prepolymers) listed earlier in this specification.
These surface active agents or emulsifiers may be made by reaction of an isocyanate with a bis(alkoxy polyethylenoxy) ester of malonic acid, and ~ay if ~esired be prepared in situ in the polyisocyanate component.
The amount of the .non-ionic, surface-active agent in tha polyisocyanate composition according to the present invention may range from 0Ol to 15 and preferably from 0.5 to 10 ~ by weight calculated on the whole composition.
From the polyisocyanate co~positions according to the present invention aqueous ~mulsions can be made, said emulsions exhibiting an improved stability and pot-life. The emulsions may comprise 99 to 25 parts by weight of water and 1 to 75 parts by weight of the polyisocyanate composition according to the present invention. Preferably they comprise 70 to 50 parts by weiqht of water and 30 to 50 parts by weight of the polyisocyanate composition. Such emulsions are made by combining the polyisocyanate composition and the water while and/or followed by thoroughly mixing at ambient temperature.
:
: SUBSTITUTE SHEET
:~
W093/03082 2 1 1 3 ~ ~ ~ PCT/GB92/01452 The emulsions may furt~er contain additives such as pigments, fillers, antioxidants, resins and plasticisers.
The emulsions are useful as adhesives, coatings, sizing-agents of paper and particularly as binders of lignocellulosic materials like woodchips and straw, in view of their excellent stability.
When the aqueous emulsions derived from the compositions of the invention are used as binders, known techniques may be employed, for example the technigues described in the afore-~entioned United Xingdom Specifications 1,444,933 and 1,523,601, EP-A-0 019 844 and E2-A-0 095 594.
The aqueous emulsions of the invention are also of particular value as binders for polyurethane foam scrap, especially flexible foam scrap which can be reconstituted for use as resilient backing for woven or tufted carpets. In a typical procedure, pieces of scrap foam are impregnated with the aqueous emulsion and the treated foam is compressed in a mould and injected with steam to promote cure.
The invention is il~ustrated but not limited by the following Examples in which all parts and percentages are by weight.
Exam~le 1 A prepolymer having an NCO content of 13.7 % was prepared by reacting 62 parts of an isocyanate with a ure~onimine content SUBSTITUTE SHEET
W093/03082 PCT/GB92/014~2 2113'13~ - lO-of 16.4 ~ with 35 parts of castor oil and 3 parts of the monomethyl ether of polyethylene glycol having a molecular weight of 750.
A 30 % aqueous emulsion was prepared. The initial NCO content was measured and the change in NCO content then monitored during subsequent storage of the emulsion :
NCO content Initial 4~1 %
15 mins 3.6 %
45 mins 3.2 % Reduction of NCO content 100 mins 3.2 % at 180 minutes - 27 % (interpola~ion) 300 mins 2.6 %
Exam~le 2 A pxepolymer having an NCO content of 13.7 ~ W~5 prepared as described in Example 1. A 47 % emulsion of the prepolymer in water, containing 5 % of butyl benzyl phthalate, was prepared.
Initial and subsequent NCO contents were found to be as follows :
~CO conten~
Initial 6.1 %
6~ mins 6.1 ~ Reduction of NCO content 120 mins 5.1 % at 180 ~inutes = 15 % (extrapolation) 2113~33 Emulsion stability was better than in Example 1.
Exam~le 3 A prepolymer having an NC0 content of 13.0 % was prepared by reacting 54 pts of an i~ocyanate having a uretonimine content of 16.4 % with 24.5 pts of castor oil, 8.5 pts of poly bdR-45HT, (a hydroxyl terminated polybutadiene resin with a molecular weight of 2500), 10 pt- of butyl benzyl phthalate and 3 pts of the monomethyl ether of polyethylene glycol having a ~: mo}ecular weight of 750.
A 40 % aqueous emulsion was prepared. Initial and ~ubseguent :NQ0 contents were foùnd to be as follows : _ NC0 content.
Initial 5.2 %
30 mins 4.8 % Reduction of NC0 content 200 mins 4.2 S at 180 minutes - 21 % (interpolation) 1440 ~ins 1.0 ~: ~
:
ExamDle 4 A prepolymer having an NC0 content of 12.8 % was prepared by reacting 54 pts of an isocyanate haYing a uretonimine content of 16.4 % with 24.5 pts of castor oil, 8.5 pts of ~erathane 2000 (a polytetramethylene ether glycol of molecular weight 20Q0 : Terathane is a Registered Trade Mark), 10 pts of butyl benzyl phthalate and 3.0 pts of the monomethyl ether of polgethylene glycol having a molecular weight of 750.
-, , ~ ~.
SUBSTITUTE SHEET
A 40 % aqueous emulsion was prepared. Initial and subsequent NC0 contents were found to be as follows :
NCO content Initial 5.14 %
25 mins 4.6 % Reduction of NC0 content 90 mins 4.2 ~ at 180 minutes = 32 ~ (extrapolation) 160 mins ~.6 %
* product precipitating and foaming Comparison Example 5 A prepolymer having an NC0 content of 17.6 % was prepared by reacting 65.5 pts of~Suprasec 1042 (a commercially available emulsifiable polyisocyanate containing no uretonimine-mo~ified polyisocyanate components) with 34.5 pts of a 2000 ~olecular weight polypropylene glycol diol. (5uprasec is a Reqistered Trademar~).
A 30 % aqueous emulsion was prepared. The initial and subsequent NC0 contents were found to be as follows :
O con~ent Initial 5.3 %
lO mins 4.8 % Reduction of NC0 content 30 mins 3.9 % at 180 minutes = 93 %
45 mins 2.9 %
180 mins 0.35 SUBSTITUTE S~4EET
Comparison of the reduction in NCo content on storage of a~
emulsion derived from a non-uretonimine modified emulsifiable polyisocyanate (Example 5) with those observed for emulsions prepared from polyisocyanates according to the invention shows a substantial improvement in pot-life for the invention compositions.
Aqueous emulsions derived from the invention compositions, when used as binders for foam scrap, yield foam composites having good properties, as shown in Table I. Properties of a foa~
composite derived from a standard toluene diisocyanate (TDI) prepolymer (TDI, 3000 molecular weight polypropylene glycol, triol and mineral oil) are reported in Table I for comparison purposes.
~ ~ SUBSTlTUTE SHEET
:
WO 93/03082 PCI`/GB92/014~2 2 1 1 3 ~ 3 ) 14 -Table I - ProPerties of Foam Composites.
'il Oerived frcm Ellulsion ¦Deri~d fran Em~lsir~ ¦ S~ardard fo~
of Ex~nple 2 ¦of E~nple 3 ¦ derived fro~ ~DI
~ight X ai~der Le~el 4 5 6 I S 6 l 6.5 O ~it~ U U 1 80 er6ile strength (Il) ¦~ 6.9 5.3 1 ~.4 10.2 ~ 10.9 ~befor~t~on) 1~ ', j~ I
~or~ o~ to9 1~9 lt3 j 14~ 150 ~ 134 ~J~2) . I ~
t~ ) Att~r D~alic lo~ding ~_ ~2 116 1 111 _ 120 1 10t X ~o~s ~ _22 ,~ '~ 9 20.4 1 ;~0.4 _. ~ ~
Co~arisrn Orl9irel ~o) ~.9 ~ .1 6.3 6.0 ¦ 6.5 /~f~er ~k, loadinq (~ 6.~ 6.5 ~.6 6 1 5.9 6.2 ~hickness ~ X~ _~ s.r O.z 6.1 S~ 6.0 ~S211t.2) ._ I _ , _ - SVBSTITUTE S~EET
Claims (15)
1. An organic polyisocyanate composition comprising a poly-isocyanate component and a non-ionic surface active agent devoid of isocyanate-reactive groups characterised in that the polyisocyanate component comprises an isocyanate-containing reaction product of a uretonimine-modified polyisocyanate and a polyol having a molecular weight of from 500 to 10,000.
2. A composition according to claim 1 wherein the isocyanate content of the isocyanate-containing reaction product is in the range from 2 to 25 % by weight.
3. A composition according to claim 1 wherein the uretonimine content of the uretonimine-modified polyisocyanate is derived from conversion into uretonimine-modified form of 7.5 % to 60 % of the isocyanate group present in the unmodified polyisocyanate.
4. A composition according to claim 1 wherein the amount of non-ionic surface active ingredient is from 0.1 % to 15 % by weight calculated on the total composition.
5. A composition according to any one of claims 1-4 wherein the polyisocyanate component comprises an isocyanate-containing reaction product of a uretonimine-modified polyisocyanate and a polyoxypropylene or poly(oxypropylene-oxyethylene) diol or triol, or a hydroxyl-containing fatty acid ester, or a mixture thereof.
6. A composition according to any one of claims 1 to 4 wherein the uretonimine-modified polyisocyanate comprises a uretonimine-modified diphenylmethane diisocyanate.
7. A composition according to any one of claims 1 to 4 wherein the polyisocyanate component comprises a mixture of polymeric MDI and a prepolymer obtained by reacting a uretonimine-modified diphenylmethane diisocyanate with a polyoxypropylene polyol and/or castor oil.
8. A composition according to any one of claims 1 to 4 wherein the non-ionic surface active agent is a compound of the formula :
RO(CH2CH2O)nCONHX
wherein R is a C1-4 alkyl group, n is an integer such that the compound contains an average of at least 5 oxyethylene groups and X is the residue remaining after removal of an isocyanate group from an organic polyisocyanate.
RO(CH2CH2O)nCONHX
wherein R is a C1-4 alkyl group, n is an integer such that the compound contains an average of at least 5 oxyethylene groups and X is the residue remaining after removal of an isocyanate group from an organic polyisocyanate.
9. A composition according to claim 8 which is the product of reacting a polyethylenoxy alcohol of the formula :
RO(CH2CH2O)nH
wherein n is as defined in claim 8 with a large excess of a polyisocyanate component comprising an isocyanate-containing reaction product of a uretonimine-modified polyisocyanate and a polyol having a molecular weight of from 500 to 10,000.
RO(CH2CH2O)nH
wherein n is as defined in claim 8 with a large excess of a polyisocyanate component comprising an isocyanate-containing reaction product of a uretonimine-modified polyisocyanate and a polyol having a molecular weight of from 500 to 10,000.
10. A composition according to any one of claims 1 to 4 wherein the non-ionic surface active agent is a compound of the formula :
wherein X is the residue of an organic isocyanate, R1 is an alkyl group of from 1 to 4 carbon atoms, n and m are integers such that m+n is at least 10 and R, which is only present when X represents the residue of a diisocyanate or a higher functionality polyisocyanate, is an isocyanate group or a group of the formula
wherein X is the residue of an organic isocyanate, R1 is an alkyl group of from 1 to 4 carbon atoms, n and m are integers such that m+n is at least 10 and R, which is only present when X represents the residue of a diisocyanate or a higher functionality polyisocyanate, is an isocyanate group or a group of the formula
11. An aqueous emulsion comprising water and an organic polyisocyanate composition according to any one of claims 1 to 4.
12. An aqueous emulsion according to claim 11 comprising from 99 to 25 parts by weight of water and from 1 to 75 parts by weight of the organic polyisocyanate composition.
13. A method for bonding together polyurethane foam scrap which comprises impregnating the foam scrap with an aqueous emulsion according to claim 11 and compressing the treated scrap.
14. A foam composite prepared according to method of claim 13.
15. A process for the preparation of a composition according to claim 9 which comprises reacting a polyethylenoxy alcohol of formula RO(CH2CH2O)nH
wherein n is an integer such that the compound contains an average of at least 5 oxyethylene groups, with a large excess of a polyisocyanate component comprising an isocyanate-containing reaction product of a uretonimine-modified polyisocyanate and a polyol having a molecular weight of 500 to 10,000.
wherein n is an integer such that the compound contains an average of at least 5 oxyethylene groups, with a large excess of a polyisocyanate component comprising an isocyanate-containing reaction product of a uretonimine-modified polyisocyanate and a polyol having a molecular weight of 500 to 10,000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919117070A GB9117070D0 (en) | 1991-08-08 | 1991-08-08 | Polyisocyanate compositions |
| GB9117070.4 | 1991-08-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2113433A1 true CA2113433A1 (en) | 1993-02-18 |
Family
ID=10699656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002113433A Abandoned CA2113433A1 (en) | 1991-08-08 | 1992-08-05 | Polyisocyanate compositions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0597918A1 (en) |
| JP (1) | JPH06509597A (en) |
| AU (1) | AU652282B2 (en) |
| CA (1) | CA2113433A1 (en) |
| GB (1) | GB9117070D0 (en) |
| WO (1) | WO1993003082A1 (en) |
| ZA (1) | ZA925826B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5125499A (en) * | 1998-07-23 | 2000-02-14 | Huntsman Ici Chemicals Llc | Emulsifiable isocyanate compositions |
| GB0513616D0 (en) | 2005-07-04 | 2005-08-10 | Johnson Matthey Plc | Novel zirconium compound, catalyst and its use for polyurethane manufacture |
| US9683127B2 (en) * | 2012-09-28 | 2017-06-20 | Basf Se | Water-emulsible isocyanates having improved gloss |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1444933A (en) * | 1973-04-03 | 1976-08-04 | Ici Ltd | Emulsions of organic isocyanates |
| GB1523601A (en) * | 1975-03-12 | 1978-09-06 | Ici Ltd | Sheets or moulded bodies |
| DE2966876D1 (en) * | 1978-12-11 | 1984-05-10 | Ici Plc | Modified diisocyanate compositions and polyurethanes thereof |
| GB8712577D0 (en) * | 1987-05-28 | 1987-07-01 | Ici Plc | Coating compositions |
| GB8721536D0 (en) * | 1987-09-14 | 1987-10-21 | Polyvinyl Chemical Ind | Aqueous dispersions |
-
1991
- 1991-08-08 GB GB919117070A patent/GB9117070D0/en active Pending
-
1992
- 1992-08-03 ZA ZA925826A patent/ZA925826B/en unknown
- 1992-08-05 AU AU23897/92A patent/AU652282B2/en not_active Ceased
- 1992-08-05 JP JP5503426A patent/JPH06509597A/en active Pending
- 1992-08-05 EP EP92916144A patent/EP0597918A1/en not_active Withdrawn
- 1992-08-05 CA CA002113433A patent/CA2113433A1/en not_active Abandoned
- 1992-08-05 WO PCT/GB1992/001452 patent/WO1993003082A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06509597A (en) | 1994-10-27 |
| ZA925826B (en) | 1993-03-18 |
| AU2389792A (en) | 1993-03-02 |
| WO1993003082A1 (en) | 1993-02-18 |
| EP0597918A1 (en) | 1994-05-25 |
| GB9117070D0 (en) | 1991-09-25 |
| AU652282B2 (en) | 1994-08-18 |
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