CA2165507A1 - Mixtures for the production of rigid polyurethane - Google Patents
Mixtures for the production of rigid polyurethaneInfo
- Publication number
- CA2165507A1 CA2165507A1 CA002165507A CA2165507A CA2165507A1 CA 2165507 A1 CA2165507 A1 CA 2165507A1 CA 002165507 A CA002165507 A CA 002165507A CA 2165507 A CA2165507 A CA 2165507A CA 2165507 A1 CA2165507 A1 CA 2165507A1
- Authority
- CA
- Canada
- Prior art keywords
- foam
- polyisocyanate
- forming mixture
- mixture
- rigid polyurethane
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000004814 polyurethane Substances 0.000 title claims description 5
- 229920002635 polyurethane Polymers 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 20
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 4
- -1 polymethylene Polymers 0.000 claims description 16
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 14
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 10
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000006260 foam Substances 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 9
- 150000002513 isocyanates Chemical class 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 4
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000004872 foam stabilizing agent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000001408 fungistatic effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 229940113165 trimethylolpropane Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
-
- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
Mixtures which react to produce rigid polyurethane foams which are preferably present in a pressure vessel. These foam-forming mixtures contain a) a prepolymer having isocyanate groups, obtainable by reaction of a polyphenyl-polymethylene polyisocyanate containing at least three aromatic nuclei with a compound having at least two hydrogen atoms that are reactive with isocyanate groups and a molecular weight of 62 to 10,000, b) known auxiliary substances and additives, and c) a blowing agent with a boiling point below 0°C/760 mm Hg.
Description
Le A 30 719-' us / Pt/klu/S-P
~ 1 216~507 MLXlU~ES FOR TIIE PRODUCTION OF RIGID POLYURETIIANE
FOAMS
BACKGROUND OF TIIE INVENTION
The present invention relates to mixtures of at least one isocyanate prepolymer,additives, processing aids and blowing agents which are useful in the productionof rigid polyurethane foams.
It is known to prepare polyurethane one- and two-component foams by reacting 10 mixtures of polyols, foam stabilizers, plasticizers, flameproofing agents, accelerators and other auxiliary substances with diisocyanates and/or poly-isocyanates in the presence of liquefied cell-forming gases to prepolymers containing free isocyanate groups. This reaction usually takes place in pressurevessels such as aerosol cans or (for two-component foams) in pressureless two-15 chamber vessels.
During discharge of the mixture which forrns the one-component foam, the re-action mass expands by vaporization of the cell gas (frothing). By reaction withmoisture (e.g. ambient humidity), the finished foam is obtained. This finished foam can be used in a variety of ways, e.g., for filling and reinforcement purposes 20 (door frame mounting). Where two-component foam systems are used, the mix-ture is generally cured by reaction with compounds having at least two active hydrogen atoms such as cross-linking agents. Water and/or organic compounds, for example, also come into consideration as cross-linking agents.
SUMMARY OF T~E INVENTION
25 Surprisingly, it has now been discovered that concomitant use of special aromatic polyisocyanates makes it possible to prepare rigid polyurethane foams with adequate properties for practical use.
Le A 30 719-: 21655 07 `~
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to mixtures, preferably present in a pressure vessel, useful for producing rigid polyurethane foams, and cont~ining a) at least one prepolymer having isocyanate groups, obtainable by reaction of (i) a polyphenyl polymethylene polyisocyanate cont~ining at least three aromatic nuclei with (ii) compounds having at least two hydrogen atoms reactive with an isocyanate and a molecular weight of 62 to 10,000 (number average as determined by end group analysis), b) known auxiliary substances and additives and 10 c) at least one blowing agent with a boiling point below 0 C/760 mm Hg.
It is preferred that the polyphenyl polymethylene polyisocyanate containing at least three aromatic nuclei be one which is lepresenled by one or more of the following formulae:
OCN ~CH2 ~ CH2 ~ NCO
and/or OCN~CH2 ~CH2~3 (II) NCO
LeA30719 ~16~507 and/or OCN ~CH2 ~_~CH2 ~ (III) NCo In particularly preferred embodiments of the present invention, the isocyanate used to prepare the prepolymer is a mixture of a polyphenyl polymethylene poly-5 isocyanate corresponding to Formula (I), (II) andtor (III) and an aliphatic or anadditional aromatic polyisocyanate or additional polyphenyl polymethylene poly-isocyanates cont~inin3~ 4 to 10 nucleus MDI. Preferred aliphatic polyisocyanateswhich may additionally be included are hexamethylene diisocyanate and iso-phorone diisocyanate. Tolylene diisocyanate is the preferred aromatic poly-10 isocyanate to be used in addition to the polyphenyl polymethylene polyisocyanatecont~ininsJ three aromatic rings.
When a mixture of a polyphenyl polymethylene polyisocyanate having three aromatic nuclei and other k-nown isocyanates is used in the practice of the present invention, at least 15% by weight, preferably from 40 to 100% by weight, of the 15 total isocyanate present in the mixture must be the polyphenyl polymethylene polyisocyanate.
Preferred blowing agents useful in the mixtures of the present invention include:
1,1,2,2-tetrafluoroethane, difluoroethane, dimethyl ether, propane, butane, carbon dioxide, nitrous oxide and combinations thereof.
20 The present invention also relates to the rigid polyurethane foams obtained by curing the mixtures of the present invention after their outflow from a pressurevessel through the action of moisture ("one-component foams") or obtainable by curing the mixtures by reaction with compounds having molecular weights of from 18 to 6,000 and hydrogen atoms reactive with isocyanate groups as cross-linking 25 agents ("two-component foams").
Suitable cross-linking agents are known. Examples of useful cross-linking agentsinclude: water and organic polyols such as ethylene glycol, diethylene glycol, butanediol and trimethylolpropane.
LeA30719-~ 2165507 ~
The prepolymers a) to be used in the mixtures of the present invention are produced from:
1) the polyphenyl polymethylene polyisocyanates cont~inin~ at least three aromatic nuclei, optionally in combination with other known isocyanates, as described more fully above; and 2) compounds having at least h,vo hydrogen atoms that are reactive with iso-cyanate groups and having a molecular weight of from 62 to 10,000 (number average as determined by end group analysis).
Compounds having hydroxyl groups, amino groups, thiol groups or carboxyl groups, preferably compounds having llydl~yl groups, in particular compounds having 2 to 8 hydroxyl groups, especially those having molecular weights of from100 to 6000 (preferably 2000 to 6000) are useful as component 2). Specific examples of such compounds include polyethers and polyesters having at least 2, generally 2 to 8, but preferably 2 to 6 hydroxyl groups, modified vegetable oils, polycarbonates and polyesteramides. Such compounds are known to be useful for the production of homogeneous and/or cellular polyurethanes. These compounds are described, e.g., in DE-OS 2,832,253, pages 11-18. Polyethers based on tri-methylolpropane or sucrose are particularly preferred.
Compounds having hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, ple~el~bly compounds having hydroxyl groups and/or amino groups, that are usually used as chain extenders or cross-linking agents may be used during the prepal~lion of the prepolymer to be included in the foam-forming mixtures of the present invention. These chain extenders or cross-linking agents generally have 2 to 8, preferably 2 to 4, hydrogen atoms that are reactive with isocyanates. Specific examples of these are described in DE-OS 2,832,253, pages 19-20.
The prepolymers to be used in the foam-forming mixtures of the present inventionare prepared in accordance with techniques known to those skilled in the art.
The auxiliary substances and additives b) useful in the foam-forming mixtures ofthe present invention include: any of the catalysts known to be useful in poly-LeA30719-: 216~S07 r urethane forming reactions; surface-active additives, such as emulsifiers and foam stabilizers (organosilicon foam stabilizers are preferred stabilizers are generally used in an amount of from 1-5 wt.%, based on prepolymer a)); plasticizers; any of the cell regulators known to be useful in polyurethane foam-forming reactions 5 such as paraffins, fatty alcohols and dimethylpolysiloxanes; pigments or dyes;known flameproofing agents such as tricresyl phosphate; stabilizers against the effects of aging and weathering; substances with fungistatic and bacteriostatic action; and fillers.
Additional examples of suitable auxiliary substances and additives are described in DE-OS 2,732,292, pages 21-24. Further examples of surface-active additives and foam stabilizers, cell regulators, reaction inhibitors, stabilizers, inhibitors,plasticizers, flameproofing substances, dyes and fillers, substances with fungistatic and bacteriostatic action and details on methods of using and modes of action ofthese additives are described in the Kunststoff-Handbuch [Plastics Handbook], Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munchen 1966, e.g. on pages 103-113.
The blowing agents useful as component c) in the foam-forming mixtures of the present invention have a boiling point below 0C/760 mm and may be present in liquefied and/or gaseous form in the pressure vessel. Examples of such blowing agents include: 1,1,1,2-tetrafluoro-ethane (R134a), difluoroethane, dimethyl ether, propane, butane, carbon dioxide, and nitrous oxide.
The finished rigid polyurethane foam produced from the foam-forming mixtures of the present invention may be used for filling purposes (e.g., between window frames and masonry), for wall breakthroughs and reinforcement purposes (e.g., for door frame mounting).
Having thus described our invention, the following Examples are given as being illustrative thereof.
LeA3071S 2165~7 EXAMPLES
The amount indicated below for components I-IV named in each of the following Examples was charged to a moisture-free pressure vessel with continuous agitation, and the vessel was closed with a head provided with a valve. After 5 closure, a coordinated amount of cell gas was admitted under pl~s~ure. In somecases, the individual components of the cell gas mixture were admitted in succession.
In the pressure vessel, the prepolymer having isocyanate groups was formed.
After discharge of the mixture from the pressure vessel, an in~ ting foam with 10 good use properties was obtained.
Example 1 Component I 50 g polyester polyol polyether polyol propoxylated alkanolamine polyethersiloxane N-substituted morpholine Component II 110 g 3-nucleus MDI
tri(2-chloroisopropyl) phosphate Component III 22 g Blowing agent R 1 34a ( 1,1,1 ,2-tetrafluoroethane) Component IV 18 g Dimethyl ether LeA30 719-~ 7 216~~
ExamPle 2 Component I 50 g polyester polyol polyether polyol S propoxylated alkanolamine polyethersiloxane N-substituted morpholine Component II I 10 g 3-nucleus MDI
tolylene diisocyanate tri(2-chloroisopropyl) phosphate Component III 22 g Blowing agent R 134 a Component IV 18 g Dimethyl ether Example 3 Component I 50 g polyester polyol polyether polyol propoxylated alkanolamine polyethersiloxane N-substituted morpholine Component II 110 g 3-nucleus MDI
hexamethylene diisocyanate tri(2-chloroisopropyl) phosphate Component III 22 g Blowing agent R 134 a Component IV 18 g Dimethyl ether Le A 30 719-21655t)7 r Example 4 Component I 50 g polyester polyol polyether polyol S propoxylated alkanolamine polyethersiloxane N-substituted morpholine Component II 110 g 3-nucleus MDI
isophorone diisocyanate tri(2-chloroisoplu~l) phosphate Component III 22 g Blowing agent R 134 a Component IV 18 g Dimethyl ether Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by 20 the claims.
~ 1 216~507 MLXlU~ES FOR TIIE PRODUCTION OF RIGID POLYURETIIANE
FOAMS
BACKGROUND OF TIIE INVENTION
The present invention relates to mixtures of at least one isocyanate prepolymer,additives, processing aids and blowing agents which are useful in the productionof rigid polyurethane foams.
It is known to prepare polyurethane one- and two-component foams by reacting 10 mixtures of polyols, foam stabilizers, plasticizers, flameproofing agents, accelerators and other auxiliary substances with diisocyanates and/or poly-isocyanates in the presence of liquefied cell-forming gases to prepolymers containing free isocyanate groups. This reaction usually takes place in pressurevessels such as aerosol cans or (for two-component foams) in pressureless two-15 chamber vessels.
During discharge of the mixture which forrns the one-component foam, the re-action mass expands by vaporization of the cell gas (frothing). By reaction withmoisture (e.g. ambient humidity), the finished foam is obtained. This finished foam can be used in a variety of ways, e.g., for filling and reinforcement purposes 20 (door frame mounting). Where two-component foam systems are used, the mix-ture is generally cured by reaction with compounds having at least two active hydrogen atoms such as cross-linking agents. Water and/or organic compounds, for example, also come into consideration as cross-linking agents.
SUMMARY OF T~E INVENTION
25 Surprisingly, it has now been discovered that concomitant use of special aromatic polyisocyanates makes it possible to prepare rigid polyurethane foams with adequate properties for practical use.
Le A 30 719-: 21655 07 `~
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to mixtures, preferably present in a pressure vessel, useful for producing rigid polyurethane foams, and cont~ining a) at least one prepolymer having isocyanate groups, obtainable by reaction of (i) a polyphenyl polymethylene polyisocyanate cont~ining at least three aromatic nuclei with (ii) compounds having at least two hydrogen atoms reactive with an isocyanate and a molecular weight of 62 to 10,000 (number average as determined by end group analysis), b) known auxiliary substances and additives and 10 c) at least one blowing agent with a boiling point below 0 C/760 mm Hg.
It is preferred that the polyphenyl polymethylene polyisocyanate containing at least three aromatic nuclei be one which is lepresenled by one or more of the following formulae:
OCN ~CH2 ~ CH2 ~ NCO
and/or OCN~CH2 ~CH2~3 (II) NCO
LeA30719 ~16~507 and/or OCN ~CH2 ~_~CH2 ~ (III) NCo In particularly preferred embodiments of the present invention, the isocyanate used to prepare the prepolymer is a mixture of a polyphenyl polymethylene poly-5 isocyanate corresponding to Formula (I), (II) andtor (III) and an aliphatic or anadditional aromatic polyisocyanate or additional polyphenyl polymethylene poly-isocyanates cont~inin3~ 4 to 10 nucleus MDI. Preferred aliphatic polyisocyanateswhich may additionally be included are hexamethylene diisocyanate and iso-phorone diisocyanate. Tolylene diisocyanate is the preferred aromatic poly-10 isocyanate to be used in addition to the polyphenyl polymethylene polyisocyanatecont~ininsJ three aromatic rings.
When a mixture of a polyphenyl polymethylene polyisocyanate having three aromatic nuclei and other k-nown isocyanates is used in the practice of the present invention, at least 15% by weight, preferably from 40 to 100% by weight, of the 15 total isocyanate present in the mixture must be the polyphenyl polymethylene polyisocyanate.
Preferred blowing agents useful in the mixtures of the present invention include:
1,1,2,2-tetrafluoroethane, difluoroethane, dimethyl ether, propane, butane, carbon dioxide, nitrous oxide and combinations thereof.
20 The present invention also relates to the rigid polyurethane foams obtained by curing the mixtures of the present invention after their outflow from a pressurevessel through the action of moisture ("one-component foams") or obtainable by curing the mixtures by reaction with compounds having molecular weights of from 18 to 6,000 and hydrogen atoms reactive with isocyanate groups as cross-linking 25 agents ("two-component foams").
Suitable cross-linking agents are known. Examples of useful cross-linking agentsinclude: water and organic polyols such as ethylene glycol, diethylene glycol, butanediol and trimethylolpropane.
LeA30719-~ 2165507 ~
The prepolymers a) to be used in the mixtures of the present invention are produced from:
1) the polyphenyl polymethylene polyisocyanates cont~inin~ at least three aromatic nuclei, optionally in combination with other known isocyanates, as described more fully above; and 2) compounds having at least h,vo hydrogen atoms that are reactive with iso-cyanate groups and having a molecular weight of from 62 to 10,000 (number average as determined by end group analysis).
Compounds having hydroxyl groups, amino groups, thiol groups or carboxyl groups, preferably compounds having llydl~yl groups, in particular compounds having 2 to 8 hydroxyl groups, especially those having molecular weights of from100 to 6000 (preferably 2000 to 6000) are useful as component 2). Specific examples of such compounds include polyethers and polyesters having at least 2, generally 2 to 8, but preferably 2 to 6 hydroxyl groups, modified vegetable oils, polycarbonates and polyesteramides. Such compounds are known to be useful for the production of homogeneous and/or cellular polyurethanes. These compounds are described, e.g., in DE-OS 2,832,253, pages 11-18. Polyethers based on tri-methylolpropane or sucrose are particularly preferred.
Compounds having hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, ple~el~bly compounds having hydroxyl groups and/or amino groups, that are usually used as chain extenders or cross-linking agents may be used during the prepal~lion of the prepolymer to be included in the foam-forming mixtures of the present invention. These chain extenders or cross-linking agents generally have 2 to 8, preferably 2 to 4, hydrogen atoms that are reactive with isocyanates. Specific examples of these are described in DE-OS 2,832,253, pages 19-20.
The prepolymers to be used in the foam-forming mixtures of the present inventionare prepared in accordance with techniques known to those skilled in the art.
The auxiliary substances and additives b) useful in the foam-forming mixtures ofthe present invention include: any of the catalysts known to be useful in poly-LeA30719-: 216~S07 r urethane forming reactions; surface-active additives, such as emulsifiers and foam stabilizers (organosilicon foam stabilizers are preferred stabilizers are generally used in an amount of from 1-5 wt.%, based on prepolymer a)); plasticizers; any of the cell regulators known to be useful in polyurethane foam-forming reactions 5 such as paraffins, fatty alcohols and dimethylpolysiloxanes; pigments or dyes;known flameproofing agents such as tricresyl phosphate; stabilizers against the effects of aging and weathering; substances with fungistatic and bacteriostatic action; and fillers.
Additional examples of suitable auxiliary substances and additives are described in DE-OS 2,732,292, pages 21-24. Further examples of surface-active additives and foam stabilizers, cell regulators, reaction inhibitors, stabilizers, inhibitors,plasticizers, flameproofing substances, dyes and fillers, substances with fungistatic and bacteriostatic action and details on methods of using and modes of action ofthese additives are described in the Kunststoff-Handbuch [Plastics Handbook], Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munchen 1966, e.g. on pages 103-113.
The blowing agents useful as component c) in the foam-forming mixtures of the present invention have a boiling point below 0C/760 mm and may be present in liquefied and/or gaseous form in the pressure vessel. Examples of such blowing agents include: 1,1,1,2-tetrafluoro-ethane (R134a), difluoroethane, dimethyl ether, propane, butane, carbon dioxide, and nitrous oxide.
The finished rigid polyurethane foam produced from the foam-forming mixtures of the present invention may be used for filling purposes (e.g., between window frames and masonry), for wall breakthroughs and reinforcement purposes (e.g., for door frame mounting).
Having thus described our invention, the following Examples are given as being illustrative thereof.
LeA3071S 2165~7 EXAMPLES
The amount indicated below for components I-IV named in each of the following Examples was charged to a moisture-free pressure vessel with continuous agitation, and the vessel was closed with a head provided with a valve. After 5 closure, a coordinated amount of cell gas was admitted under pl~s~ure. In somecases, the individual components of the cell gas mixture were admitted in succession.
In the pressure vessel, the prepolymer having isocyanate groups was formed.
After discharge of the mixture from the pressure vessel, an in~ ting foam with 10 good use properties was obtained.
Example 1 Component I 50 g polyester polyol polyether polyol propoxylated alkanolamine polyethersiloxane N-substituted morpholine Component II 110 g 3-nucleus MDI
tri(2-chloroisopropyl) phosphate Component III 22 g Blowing agent R 1 34a ( 1,1,1 ,2-tetrafluoroethane) Component IV 18 g Dimethyl ether LeA30 719-~ 7 216~~
ExamPle 2 Component I 50 g polyester polyol polyether polyol S propoxylated alkanolamine polyethersiloxane N-substituted morpholine Component II I 10 g 3-nucleus MDI
tolylene diisocyanate tri(2-chloroisopropyl) phosphate Component III 22 g Blowing agent R 134 a Component IV 18 g Dimethyl ether Example 3 Component I 50 g polyester polyol polyether polyol propoxylated alkanolamine polyethersiloxane N-substituted morpholine Component II 110 g 3-nucleus MDI
hexamethylene diisocyanate tri(2-chloroisopropyl) phosphate Component III 22 g Blowing agent R 134 a Component IV 18 g Dimethyl ether Le A 30 719-21655t)7 r Example 4 Component I 50 g polyester polyol polyether polyol S propoxylated alkanolamine polyethersiloxane N-substituted morpholine Component II 110 g 3-nucleus MDI
isophorone diisocyanate tri(2-chloroisoplu~l) phosphate Component III 22 g Blowing agent R 134 a Component IV 18 g Dimethyl ether Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by 20 the claims.
Claims (10)
1. A rigid polyurethane foam-forming mixture comprising:
a) a prepolymer having free isocyanate groups obtained by reacting (i) a polyphenyl-polymethylene polyisocyanate containing at least three aromatic nuclei with (ii) a compound having at least two hydrogen atoms that are reactive with isocyanate groups and a molecular weight of 62 to 10,000, b) auxiliary substances and additives, and c) a blowing agent with a boiling point below 0 °C/760 mm Hg.
a) a prepolymer having free isocyanate groups obtained by reacting (i) a polyphenyl-polymethylene polyisocyanate containing at least three aromatic nuclei with (ii) a compound having at least two hydrogen atoms that are reactive with isocyanate groups and a molecular weight of 62 to 10,000, b) auxiliary substances and additives, and c) a blowing agent with a boiling point below 0 °C/760 mm Hg.
2. The mixture of Claim 1 in which the polyisocyanate a)(i) is a polyiso-cyanate based on methylene diphenyl diisocyanate (MDI) and may be represented by one or more of the following formulae:
(I) and/or (II) and/or (III)
(I) and/or (II) and/or (III)
3. The foam-forming mixture of Claim 1 in which polyisocyanate a)(i) is a mixture of the polyphenyl polymethylene polyisocyanate containing at least three aromatic nuclei and an aliphatic or an aromatic polyisocyanate other than the polyphenyl polymethylene polyisocyanate containing at least three aromatic nuclei.
4. The foam-forming mixture of Claim 3 in which tolylene diisocyanate is included in polyisocyanate a)(i).
5. The foam-forming mixture of Claim 3 in which hexamethylene diiso-cyanate is included in polyisocyanate a)(i).
6. The foam-forming mixture of Claim 3 in which isophorone diisocyanate is included in polyisocyanate a)(i).
7. The foam-forming mixture of Claim 1 in which blowing agent c) is selected from 1,1,1,2-tetrafluoroethane, difluoroethane, dimethyl ether, propane, butane, carborn dioxide, nitrous oxide, and combinations thereof.
8. A pressure vessel containing the foam-forming mixture of Claim 1.
9. A rigid polyurethane foam obtained by curing the foam-forming mixture of Claim 1.
10. A rigid polyurethane foam obtained by reacting the foam-forming mixture of Claim 1 with a cross-linking agent having a molecular weight of from 18 to 6,000 and reactive hydrogen atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4445281A DE4445281A1 (en) | 1994-12-19 | 1994-12-19 | Mixtures leading to hard polyurethane foams |
| DEP4445281.0 | 1994-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2165507A1 true CA2165507A1 (en) | 1996-06-20 |
Family
ID=6536264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002165507A Abandoned CA2165507A1 (en) | 1994-12-19 | 1995-12-18 | Mixtures for the production of rigid polyurethane |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0718331A2 (en) |
| JP (1) | JPH08231671A (en) |
| CA (1) | CA2165507A1 (en) |
| DE (1) | DE4445281A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19829103B4 (en) * | 1998-06-30 | 2009-12-10 | Rathor Ag | Prepolymer mixture for the production of polyurethane insulating foams and their use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2732292A1 (en) | 1977-07-16 | 1979-02-01 | Bayer Ag | METHOD FOR MANUFACTURING POLYURETHANE PLASTICS |
| DE2832253A1 (en) | 1978-07-22 | 1980-01-31 | Bayer Ag | METHOD FOR PRODUCING MOLDED FOAMS |
-
1994
- 1994-12-19 DE DE4445281A patent/DE4445281A1/en not_active Withdrawn
-
1995
- 1995-12-06 EP EP95119169A patent/EP0718331A2/en not_active Withdrawn
- 1995-12-18 CA CA002165507A patent/CA2165507A1/en not_active Abandoned
- 1995-12-18 JP JP7347494A patent/JPH08231671A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08231671A (en) | 1996-09-10 |
| EP0718331A2 (en) | 1996-06-26 |
| DE4445281A1 (en) | 1996-06-20 |
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