GB2039780A - Aqueous emulsions of isocyanates, their preparation and their use as binders, adhesives and surface coatings - Google Patents
Aqueous emulsions of isocyanates, their preparation and their use as binders, adhesives and surface coatings Download PDFInfo
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- GB2039780A GB2039780A GB7942313A GB7942313A GB2039780A GB 2039780 A GB2039780 A GB 2039780A GB 7942313 A GB7942313 A GB 7942313A GB 7942313 A GB7942313 A GB 7942313A GB 2039780 A GB2039780 A GB 2039780A
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- aqueous emulsion
- ethylene oxide
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- 239000000839 emulsion Substances 0.000 title claims abstract description 51
- 239000011230 binding agent Substances 0.000 title claims abstract description 7
- 239000012948 isocyanate Substances 0.000 title claims description 29
- 150000002513 isocyanates Chemical class 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000000853 adhesive Substances 0.000 title abstract description 4
- 230000001070 adhesive effect Effects 0.000 title abstract description 4
- 238000000576 coating method Methods 0.000 title abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 35
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 33
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 28
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 26
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 229920001400 block copolymer Polymers 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 6
- 229920013818 hydroxypropyl guar gum Polymers 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 230000003019 stabilising effect Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 abstract description 5
- 238000005189 flocculation Methods 0.000 abstract description 4
- 230000016615 flocculation Effects 0.000 abstract description 4
- 239000011093 chipboard Substances 0.000 abstract description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 239000002562 thickening agent Substances 0.000 description 10
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000012978 lignocellulosic material Substances 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- -1 tetramethylene pentamine Chemical compound 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- PGYPOBZJRVSMDS-UHFFFAOYSA-N loperamide hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)N(C)C)CCN(CC1)CCC1(O)C1=CC=C(Cl)C=C1 PGYPOBZJRVSMDS-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000731961 Juncaceae Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- WMTLVUCMBWBYSO-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 WMTLVUCMBWBYSO-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WIJRMGQOERPOJA-UHFFFAOYSA-N benzyl cyanate Chemical compound N#COCC1=CC=CC=C1 WIJRMGQOERPOJA-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- YTSACTNRGUJEGO-UHFFFAOYSA-N oxirane prop-1-ene Chemical compound CC=C.C1CO1 YTSACTNRGUJEGO-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
-
- 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
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Aqueous emulsions of organic polyisocyanates, especially mixtures of methylene bridged polyphenyl polyisocyanates (MDI), use as surface active agents block copolymers of propylene oxide and ethylene oxide having at least two copolymer chains at least one of the chains having a propylene oxide-derived group of M.wt. at least 400 and each chain containing 10-90% wt. of ethylene oxide. The block copolymers are preferably condensed on hexamethylene diamine (HMD), especially those in which each of the four chains comprises an ethylene oxide residue attached to the HMD followed by a propylene oxide group of molecular weight at least 400 followed by an ethylene oxide group of size such that the chain contains 10-90% wt. ethylene oxide. Any flocculation is prevented by adding polyethylene oxide or hydroxypropyl guar gum. The emulsions are useful as binders, e.g. in chipboard manufacture, adhesives and surface coatings.
Description
SPECIFICATION
Aqueous emulsions of isocyanates, their preparation and their use as binders, adhesives and
surface coatings
Aqueous emulsions of organic isocyanates have previously been prepared which are stable, by
which it is meant that they do not separate into discrete layers of their main components. Such
emulsions, however, are difficult to use for some applications due to gelling which results from the
reaction between the water and the isocyanate to form a polyurea. This leads to a reduction in the time
during which the emulsions remain workable, such time being frequently referred to as 'pot'life. Stable
isocyanate emulsions of adequate 'pot'life in which the surfactant used to achieve stability is admixed
with the isocyanate prior to emulsification are described in UK Patent Specification No. 1444933.
It has, however, proved difficult hitherto to prepare stable isocyanate emulsions of adequate
'pot'life when the surfactant is incorporated into the aqueous phase rather than into the organic phase
prior to emulsification.
According to the present invention there is provided an aqueous emulsion comprising an organic
polyisocyanate and a surface-active agent which is a block copolymer of propylene oxide and ethylene
oxide having at least two copolymer chains, at least one of the chains having a propylene oxide moeity
of molecular weight at least 400, preferably at least 800, and each chain containing 1090% by weight of ethylene oxide.
The block copolymer is preferably condensed on a chemical substrate which is a molecule other than an isocyanate or a mixture of such molecules containing at least two, preferably at least three, sites
capable of reaction with alkylene oxides. Preferred chemical substrates include amines, for example an
oligomeric ethyleneimine, ethylene diamine, diethylene triamine, triethylene tetra-amine, tetramethylene
pentamine, dihexamethylene triamine, N-alkyl propylene diamine and especially hexamethylene
diamine.
Mixtures of amines may be used for example a mixture of amines from hexamethylene diamine
production which contain a mixture of amines of general formula H2N(CGHr2NH)nC6H,2 where "n" is zero
or an integer from 1 to 30.
Preferred surface active agents for use in the invention have an ethylene oxide group at the free
end of each copolyer chain; in more preferred surface active agents the copolymer chain is also attached to the chemical substrate, especially when the substrate is hexamethylene diamine, by an ethylene
oxide group, especially an ethylene oxide group having a low molecular weight, for example a group
containing less than six ethylene oxide residues. Especially preferred surface active agents are those in
which hexamethylene diamine is attached to four chains, each chain comprising an ethylene oxide
group containing one or two ethylene oxide residues attached directly to the amine, followed by a
propylene oxide group which in turn is followed by an ethylene oxide group at the free end of the chain.
The most useful surface active agents for use in the invention may be represented by the formula
(H ExPvEz)2N(CH2)6N(EzPvExH)2 where - N(CH2)e is a hexamethylene diamine residue
E is an ethylene oxide residue
P is a propylene oxide residue
H is hydrogen
Z is an integer between 1 and 6
Y is an integer between 7 and 500, preferably 1 5 to 80
X is an integer between 1 and 500, preferably 5 to 200
Surface active agents for use in the invention in which the chemical substrate for the block
copolymer chains is an amine mey be prepared by known techniques for amines; for example hexamethylene diamine, ethylene oxide and propylene oxide may be reacted so that the alkylene oxides are added alternately in the desired order to build up the molecule required.
Organic polyisocyanates include di-isocyanates, particularly aromatic di-isocyanates, and isocyanates of higher functionality.
Examples of organic polyisocyanates which may be used in the invention include aliphatic
isocyanates such as hexamethylene di-isocyanates, aromatic isocyanates such as m- and pphenylene di-isocyanate, tolylene -2,4- and 2,6 diisocyanates, diphenylmethane-4,4'-diisocyanate, chlorophenylene-2,4-diisocyanate, naphthylene 1 ,5-diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'- diisocyanate-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate and diphenyl ether diisocyanate, cycloaliphatic diisocyanates such as cyclohexane-2,4- and 2,3-dissocyanates, 1-methyl cyclohexyl-2,4- and 2,6-diisocyanates and mixtures thereof and bis-(isocyanato cyclohexyl-) methane and tri-isocyanates such as 2,4,6-trilso cyanatotoluene and 2,4,4'-triisocyanatodiphenylether.
Mixtures of isocyanates may be used, for example a mixture of tolylene diisocyanate isomers such as the commerciaily available mixtures of 2,4- and 2,6-isomers and also the mixture of di- and higher poly-isocyanates produced by phosgenation of aniline/formaldehyde condensates. Such mixtures are well-known in the art and include the crude phosgenation products containing mixtures of methylene bridged polyphenyl polyisocyanates, including diisocyanate, triisocyanate and higher polyisocyanates together with any phosgenation by-products.
Preferred polyisocyanates to be used in the present invention are those wherein the isocyanate is an aromatic diisocyanate or polyisocyanate of higher functionality in particular crude mixtures of methylene bridged polyphenyl polyisocyanates containing diisocyanates, triisocyanate and higher functionatity polyisocyanates. Methylene bridged polyphenyl polyisocyanates are well known in the art and have the generic formula
where n is one or more and in the case of the crude mixtures represents an average of more than one.
They are prepared by phosgenation of corresponding mixtures of polyamines obtained by condensation of aniline and formaldehyde. For convenience, crude mixtures of methylene bridged polyphenyl polyisocyanates containing diisocyanate, triisocyanate and higher functionality polyisocyanates are referred to hereinafter as MDI.
Other organic isocyanates which can be used in the invention include isocyanate-ended prepolymers made by reaction of an excess of a diisocyanate or higher functionality polyisocyanate with a hydroxyl-ended polyester or hydroxyl-ended polyether and products obtained by reacting an excess of diisocyanate or higher functionality polyisocyanate with a monomeric polyol or mixture of monomeric polyols such as ethylene glycol, trimethylol propane or butane-diol. Of particular value, however, because of their slower reaction with water, are isocyanate-ended prepolymers prepared using hydrophobic polyols such as castor oil.
One class of isocyanate-ended prepolymers which may be used are the isocyanate-ended prepolymers of MDI.
The emulsions according to the invention are of the oil in water type and preferably comprise from 90 parts to 40 parts by weight of water, from 10 parts to 60 parts by weight of organic polyisocyanate and a stabilising amount of surface active agent hereinbefore described. A preferred amount of the surface active agent is from 0.1% by weight to 10% by weight especially 1-2.5% by weight based on the water present.
Emulsions comprising approximately equal parts by weight of water and organic polyisocyanate are useful for most applications.
The invention further provides a process for preparing an aqueous emulsion comprising an organic polyisocyanate comprising the step of mixing an organic polyisocyanate, eg. as hereinbefore described with water in the presence of a surface active agent as hereinbefore described. Preferably the surface active agent is applied as a solution or dispersion in water, conveniently by dissolving or dispersing the surface active agent in the whole, or a part, of the water used in preparing the emulsion. Mixing of the organic polyisocyanate with the water may be carried out by any means which is appropriate for emulsification. Either high shear or low shear mixing may be used.
In preferred processes according to the invention from 10 parts to 60 parts by weight of organic polyisocyanate are mixed with 90 to 40 parts by weight of water in the presence of a stabilising amount of the surface active agent. A preferred amount of surface active agent is from 0, 1% to 1 0% by weight based on the water present in the final emulsion.
The emulsions are suitably prepared at temperatures in the range SOC to 40 C preferably 1 50C to 250C especially under ambient temperature conditions.
Optionally, emulsions according to the invention may advantageously comprise a thickening agent additional to the surface active agents described hereinbefore. Such thickeners are useful in assisting the prevention of any tendency for the emulsions to flocculate. Preferred thickeners are polyethylene oxide and hydroxypropyl guar gum. Thickening agents may preferably be present at a concentration of 0.01% to 1% by weight especially 0.1% to 0.4% by weight based on the water present. Conveniently, the thickeners are incorporated into the emulsions dissolving or dispersing them in water, which may be the whole, or part, of the water used in preparing the emulsion.
The invention further provides aqueous compositions for the emulsification of organic polyisocyanates comprising water and a surface active agent as hereinbefore described.
In yet a further embodiment of the invention there is provided an aqueous composition for the emulsification of organic polyisocyanates comprising water, a surface active agent as hereinbefore described and a thickener, preferably polyethylene oxide or hydroxypropyl guar gum.
Such aqueous compositions preferably contain 91 parts to 55 parts by weight of water and 8 parts to 40 parts by weight of surface active agent, and 1 part to 5 parts by weight of a thickener when present.
Dilute compositions, for example those containing 98.5 parts to 95 parts by weight of water and 1.5 parts to 5 parts by weight of surface active agent and (when present) 0.2 parts to 1 part by weight of thickener may conveniently be used as they stand for emulsifying the organic polyisocyanate. Such dilute solutions may be concentrated, for example by evaporation, to an extent such that preferably no solid phase appears. A concentration factor of up to 1 5 times is convenient for the concentration of most dilute compositions. Concentrated compositions may be diluted appropriately with water to produce composition of a strength suitable for emulsification of the organic polyisocyanate.
As mentioned hereinbefore, aqueous emulsions of organic polyisocyanates eventually degrade, for example by gelling due to reaction between the water and the isocyanate to form a polyurea. While the aqeuous emulsions of the present invention have the advantage that little gelling apparently occurs at ambient temperature and therefore pot-life is very long, the invention contemplates further a two-pack system comprising a first composition comprising water, a surface active agent as hereinbefore described and optionally comprising a thickener as hereinbefore described and a second composition comprising an organic polyisocyanate as hereinbefore described in which each composition is adapted to be mixed with the otherjust prior to use.
The emulsions of the present invention are useful as adhesives, binders and surface coatings.
Examples of suitable applications are given in UK Patent Specification Nos. 1,444,933 and 1,502,777.
In our pending UK Patent Specification No. 1 523601 there is described and claimed a process for manufacturing sheets or moulded bodies, especially chipboard, which comprises hot pressing a mass of lignocellulosic material mixed with a binding agent comprising an aqueous emulsion of an organic polyisocyanate. The emulsions of the present invention are particularly useful for this application where delays of a few hours in pressing can occur.
Thus according to a further aspect of our invention we provide a process for manufacturing sheets or moulded bodies comprising hot pressing a mass of lignocellulosic material mixed with an aqueous emulsion of the invention.
Lignocellulosic material which can be used in the process includes wood chips, wood fibres, shavings, wood wool, cork and bark, sawdust and like waste products from the woodworking industry, and/or fibres from other natural products which are lignocellulosic for example bagasse, straw, flax residues and dried rushes, reeds and grasses. Additionally, there may be mixed with the lignocellulosic material inorganic flake or fibrous material e.g. glass fibre, mica or asbestos.
The process is conveniently carried out by spraying the lignocellulosic material with the emulsion while it is being tumbled in a mixer. The sprayed chips are allowed to fall evenly onto a steel platen coated with a release agent and pressed at a temperature of from 1 50 to 2209C. The isocyanate emulsion may be used in conjunction with other binders such as the resin glues or paraffin wax emulsions commonly used for chipboard manufacture. It may also be used in admixture with, for example, ureaformaldehyde resin glue. A useful mixture comprises 2 to 3 parts urea-formaldehyde and 1 part of emulsified isocyanate. Reaction of the isocyanate with the strong base in phenol-formaldehyde resin glues and with the amine groups in melamine/urea-formaldehyde resin glues makes these mixtures impractical.Additives and adjuvants commonly used in isocyanate compositions may be incorporated in the emulsions as desired. Pigments, fillers, antioxidants, resins and plasticisers are examples. Hydrophobic diluents may be useful in further slowing down the rate of reaction.
The invention is illustrated by, but not limited to, the following Examples No. 1 to 20.
EXAMPLES 1-16 A range of surface active agents derived from hexamethylene diamine was evaluated in the preparation of emulsions of an organic isocyanate. The surface active agents had the general formula (HExPvE2)2N(CH2)6N(EzPvExH)2 as hereinbefore described and in which Z was 1 throughout the series, X and Y being varied. The isocyanate emulsified was an MDI prepolymer (Suprasec DNR available from Imperial Chemical
Industries Ltd.).
The emulsions were prepared by dissolving 2.5 parts by weight of the surface active agent in 1 00 parts by weight of water at 200 C. adding 100 parts by weight of the isocyanate and mixing. Two modes of mixing were tested, firstly medium stirring at 2000 revolutions per minute for 2 minutes (referred to as low energy stirring) and secondly high speed homogenising at 10,000 revolutions for 1 minute (referred to as high energy stirring) The quality of dispersion of the emulsion was noted visually and given a rating on a 1-10 scale, on which 10 was a creamy dispersion, 8 a very fine dispersion, 6 a fine dispersion, 4 a coarse dispersion and 2 a very coarse dispersion. The emulsions were allowed to stand at room temperature for several days and the pot performance i.e. the tendency for flocculation, settling or gelling noted.Such tendencies were again given ratings on a 1-10 scale, on which 10 indicated no flocculation settling or gelling over the time of observation, 5 indicated that flocculation was apparent and some gelling had occured and 1 indicated rapid flocc.ulation with gelling within less than one hour.
The results are shown in Table 1.
TABLE I
Surface Action Agent Composition Dispersion Pot Example Stirring Quality Performance No. Y X Energy (1-10) (1-10) 1 62 34 High 8 7 2 " | 53 1 8 7 3 " 80 .. 9 8 4 " 120 It 9 8 5 | " | 150 | " | 10 | 9 6 .. 34 Low 8 7 7 | " | 53 | " | 8 | 7 8 .. 80 " 8 7 9 " 120 " 9 8 10 " 150 " 10 9 11 92 83 High 9 8 12 | " | 187 | " | 10 | 8 13 .. 290 .. 10 8 14 92 83 Low 6 5 15 .. 187 .. 7 6 16 | " | 290 | " | 7 | 6 EXAMPLES 17-20 Examples 4, 5, 13 and 10 respectively were repeated with the difference that 0.2 parts by weight of polyethylene oxide thickener Polyox WSR 205 ex Union Carbide Inc.) were added to the aqueous solution of surface active agent before addition of the isocyanate. The results obtained are shown in
Table 2.
TABLE 2
Surface Action Agent Composition Dispersion Pot Example Stirring Quality Performance No. Y X Energy (1-10) (1-10) 1 62 120 High 9 10 2 62 150 High 10 10 3 92 290 High 10 10 4 62 150 Low 10 10 COMPARATIVE EXAMPLES 21-29 For the purposes of comparison with Examples 1-16 aqueous emulsions of the same isocyanate (Suprasec DNR) were prepared under similar conditions using different surface active agents based on alkylene oxides and using various chemical substrates which did not fall within the class required by the present invention either by virtue of containing ethylene oxide without propylene oxide, or by virtue of having only one copolymer chain of ethylene oxide/propylene oxide. Table 3 shows the results obtained.
TABLE 3
Moles Moles No. of of of Alkylene Dispersion Pot Example Chemical Propylene Ethylene Oxide Stirring Quality Performance No. Substrate Oxide Oxide Chains Energy (1-10) (1-10) 1 Nonyl phenol - 10 High 9 3 2 ,, - 5 High 1 1 3 .. - 10 Low 3 3 4 Stearylamine - 20 High 4 3 5 ,, 20 Low 3 3 6 Nonyl phenol 7 30 One High 8 1 7 Methanol 39 120 One High 7 '3 8 ,, 30 65 One High 8 4 9 " 30 65 One Low 5 3
Claims (17)
1. An aqueous emulsion comprising an organic polyisocyanate and a surface-active agent which is a block copolymer of propylene oxide and ethylene oxide having at least two copolymer chains, at least one of the chains having a propylene oxide moecity of molecular weight at least 400 and each chain containing 10 to 90% by weight of ethylene oxide.
2. An aqueous emulsion according to claim 1 in which the block copolymer is condensed on a chemical substrate which is a molecule other than an isocyanate or a mixture of such molecules containing at least two sites capable of reaction with alkylene oxides.
3. An aqueous emulsion according to claim 2 in which the chemical substrate is an amine.
4. An aqueous emulsion according to claim 3 in which the amine is hexamethylene diamine.
5. An aqueous emulsion according to any one of claims 2 to 4 in which each copolymer chain has an ethylene oxide group at the free end of said chain.
6. An aqueous emulsion according to claim 5 in which each copolymer chain is attached to the chemical substrate by an ethylene oxide group.
7. An aqueous emulsion according to claim 6 in which the ethylene oxide group attached to the chemical substrate contains less than six ethylene oxide residues.
8. An aqueous emulsion according to claim 4 in which the hexamethylene diamine is attached to four copolymer chains, each of said chains comprising an ethylene oxide group containing one or two ethylene oxide residues attached directly to the hexamethylene diamine followed by a propylene oxide group which in turn is followed by an ethylene oxide group at the free end of the chain.
9. An aqueous emulsion according to any one of claims 4 to 8 comprising a surface active agent which has the formula (HExPvEz)2N(CH2)0N(EzPvRxH)2 wherein N(CH2)5N is a hexamethylene diamine residue, E is an ethylene oxide residue, P is a propylene oxide residue, H is hydrogen, z in an integer between 1 and 6, y is an integer between 7 and 500 and x is an integer between 1 and 500.
10. An aqueous emulsion according to any one of the preceding claims comprising from 90 parts to 40 parts by weight of water, from 10 parts to 60 parts by weight of the organic polyisocyanate and a stabilising amount of the surface active agent.
1 An aqueous emulsion according to claim 10 in which the amount of surface active agent is from 0.1% by weight to 10% by weight based on the water present.
12. An aqueous emulsion according to any one of the preceding claims comprising polyethylene oxide or hydroxypropyl guar gum.
13. An aqueous emulsion according to claim 12 in which the polyethylene oxide or hydroxypropyl guar gum is present at a concentration of from 0.01% to 1% by weight based on the water present.
14. An aqueous emulsion according to claim 1 as hereinbefore described with particular reference to any one of Examples 1 to 20.
15. A process for the preparation of an aqueous emulsion as claimed in any one of claims 1 to 1 4 comprising the step of mixing the organic polyisocyanate with water in the presence of the surfaceactive agent.
16. A process as claimed in claim 1 5 in which the surface-active agent is dissolved or dispersed in the whole, or part, of the water and the resulting solution or dispersion mixed with the polyisocyanate.
17. The use of an aqueous emulsion as claimed in any one of claims 1 to 14 as a binder for manufacturing sheets or moulded bodies of lignocellulose material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7942313A GB2039780A (en) | 1978-12-22 | 1979-12-07 | Aqueous emulsions of isocyanates, their preparation and their use as binders, adhesives and surface coatings |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7849783 | 1978-12-22 | ||
| GB7942313A GB2039780A (en) | 1978-12-22 | 1979-12-07 | Aqueous emulsions of isocyanates, their preparation and their use as binders, adhesives and surface coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2039780A true GB2039780A (en) | 1980-08-20 |
Family
ID=26270074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7942313A Withdrawn GB2039780A (en) | 1978-12-22 | 1979-12-07 | Aqueous emulsions of isocyanates, their preparation and their use as binders, adhesives and surface coatings |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2039780A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57183753A (en) * | 1981-05-06 | 1982-11-12 | Mitui Toatsu Chem Inc | Novel isocyanate composition |
| GB2199333A (en) * | 1985-07-08 | 1988-07-06 | Dai Ichi Kogyo Seiyaku Co Ltd | Process for producing shaped articles from vegetable particulate materials |
| GB2221216A (en) * | 1988-07-26 | 1990-01-31 | Mobay Corp | A process for the production of fiberglass mats |
| WO1999043727A1 (en) * | 1998-02-27 | 1999-09-02 | Cytec Technology Corp. | Low voc, isocyanate based aqueous curable compositions |
-
1979
- 1979-12-07 GB GB7942313A patent/GB2039780A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57183753A (en) * | 1981-05-06 | 1982-11-12 | Mitui Toatsu Chem Inc | Novel isocyanate composition |
| JPH0258287B2 (en) * | 1981-05-06 | 1990-12-07 | Mitsui Toatsu Chemicals | |
| GB2199333A (en) * | 1985-07-08 | 1988-07-06 | Dai Ichi Kogyo Seiyaku Co Ltd | Process for producing shaped articles from vegetable particulate materials |
| GB2199333B (en) * | 1985-07-08 | 1990-07-04 | Dai Ichi Kogyo Seiyaku Co Ltd | Process for producing shaped articles from vegetable particulate materials |
| GB2221216A (en) * | 1988-07-26 | 1990-01-31 | Mobay Corp | A process for the production of fiberglass mats |
| WO1999043727A1 (en) * | 1998-02-27 | 1999-09-02 | Cytec Technology Corp. | Low voc, isocyanate based aqueous curable compositions |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |