CA2171163A1 - Low-viscosity polymer polyols, a process for producing them, and their use for the production of polyurethane foamed materials - Google Patents
Low-viscosity polymer polyols, a process for producing them, and their use for the production of polyurethane foamed materialsInfo
- Publication number
- CA2171163A1 CA2171163A1 CA002171163A CA2171163A CA2171163A1 CA 2171163 A1 CA2171163 A1 CA 2171163A1 CA 002171163 A CA002171163 A CA 002171163A CA 2171163 A CA2171163 A CA 2171163A CA 2171163 A1 CA2171163 A1 CA 2171163A1
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- Canada
- Prior art keywords
- polyol
- good
- ethylenically unsaturated
- process according
- weight
- 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
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/635—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C08G2110/0008—Foam properties flexible
Abstract
A process for producing stable, low-viscosity graft copolymer dispersions by theradical polymerisation of ethylenically unsaturated monomers in a base polyol consists of effecting the polymerisation in the presence of a polyol containing ethylenically unsaturated terminal groups and an enol ether of the following general formula A = CH-O-R
where A is a divalent radical of formula
where A is a divalent radical of formula
Description
Le A 30 960 - -FC ~ ~ 7 ~
PE/AB/S-P
Low-~ is~o~ polymer polyols, a ~l oce~ for pro~ r;n~ them. and their use for the production of polyul~ll,ane foamed materials Within the scope of the present invention, polymer polyols are understood to be products which can be obtained by the polymeric~tion of ethylenically unsaturated compounds in polyether polyols ("base polyols"). These can be used for the production of flexible polyurethane foamed m~tt-ri~l~, for example. The ethyleni-~lly unsaturated compounds which are mainly used are the monomers styrene and acrylonitrile, which may be radically polymP-ri~ed in polyether polyols as the base polyol.
The production of polymer polyols such as these is described in US Patent Specifications 3 383 351 and 3 304 273 and in DE-A 1 152 536 and DE-A 1 152 537, for example.
In the ideal case, polymer polyols are relatively low-viscosity, finely divided non-se-iimenting dispersions of the nolymer (preferably an acrylonitrile/styrene graft copolymer) in the substantially unchanged polyether polyol. The characterising features for the quality and processability of polymer polyols are their viscosity, storage stability (resistance to se~imPnt~tinn) and finely divided state. These properties are mainly influenced by the type and q~l~ntit~tive ratios of the starting m~teri~ls. In particular, the solids content (proportion of monomer in the batch) and the monomer ratio (e.g. the styrene/acrylonitrile ratio) have a considerable effect on product quality.
The most important targets when producing polymer polyols are the ~tt~inment of high solids contents (at least 40 %), with a styrene content which is as high aspossible and a viscosity which is as low as possible, and with excellent productstability at the same time.
In order to attain product stability, i.e. the suppression of unwanted agglomerated polymer particles precipitated from the continuous phase, i.e. from the base polyol, the polymer particles have to be stabilised during the production of the polymerpolyol. This stabilisation is first of all effected by the incorporation of part of the molecule of ~he base polyether in the polymer formed in situ. In this connection, the efficacy of stabilisation is firstly e.nh~n~ e~ by a molecular weight of the base polymer which is as high as possible and by the highest possible content of acrylonitrile in the monomer mixture. Whereas a high acrylonitrile content increases the intrin~ic colour of polymer polyols and the tendency towards discoloration of flexible foams produced with them, and is thus undesirable, the viscosity of polymer polyols is increased by the use of base polyols of higher molecular weights.
One possible way of obtaining low-viscosity polymer polyols having a high content of filler m~t-~ri~l~, which is subst~nti~lly independent of the molecular weight of the base polyol, is to use chain extenders in conjunction. Examples of the latter for this application include the merca~ls, halogen alkanes or alcohols which are customary in polymerisation technology.
Moreover, the use in conjunction of enol ethers as chain transfer agents is described in EP-A 008 444, due to which it is claimed to be possible to produce polymer polyols having a relatively low viscosity at a relatively high filler content and styrene content.
Another possible way of stabilising polymer polyols is the use in conjunction ofcompounds which are compatible with the polyol phase and which contain ethylenically unsaturated groups which are capable of polymerisation. These so-called macromers copolymerise with the vinyl monomers, so that the polymer particles produced are steric~lly stabilised by polyether side chains and are thus protected from agglomeration and sedimentation.
The production of polymer polyols with the use in conjunction of macromers is described in US-PS 3 652 639, US-PS 3 823 201, US-PS 4 460 715, US-PS 4 390 645, US-PS 5 093 412 and US-PS 4 342 840, for example. The ethylenically ~ 7~ ~3 unsaturated double bonds are introduced into polyether polyols, for example, by reaction with cyclic, unsaturated carboxylic acid anhydrides such as maleic anhydride and subsequent reaction with ethylene- or propylene oxide; by est~nfi~tion with acrylic or mçth~crylic acid (derivatives); by reaction with allyl glycidyl ethers; by S reaction with an unsdLul~ted isocyanate, such as an isocy~n~to~lkyl acrylate and m~th~rylate or 1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)-benæne, for example, or NCO-functional addition compounds of a polyisocyanate and hydroxyethyl or hydroxypropyl acrylate, for example.
The combination of macromers with chain transfer agents such as mercaptans or alcohols has also already been described in DE-A-2 500 274, EP-A-019 769, and inEP-A 0 091 036. Products produced using me,~ tans have the disadvantage that they mostly have an odour which is unpleasant to a greater or lesser extent.
Moreover, products such as these often do not have the desired viscosity.
Even when the aforementioned processes lead to polymer polyols which can be usedin principle as polyol components for the production of polyurethane flexible foams, further improvements are still desirable. Thus the vi~cosities taken from the literature of highly filled polymer polyols are always still quite high, particularly at high styrene contents in the monomer mixture, and smaller, agglomerated polymer particles are often observed in the run-off, i.e. the products are not sufficiently finely divided.
It has now surprisingly been found that polymer polyols which are free from agglomerates and which have high filler contents and low viscosities can be produced by producing the polymer polyols in the presence of a macromer of the type described above and an enol ether of general formula A=CH-O-R
where 2 ~a 7 1 I ~ ~
A is a divalent radical of formula R~ ~
R ,~resents a C, l8 alkyl, C5 ,0 cycloalkyl or optionally a benzyl radical with a substituted nucleus, and R' represents hydrogen or a C, 8 alkyl radical.
By the use in conjunction of a combination of macromers with special chain transfer agents of the enol ether type as described above, stable, finely divided polymerpolyols become ~ccçs~ible, as shown in the comparative examples, which have lower viscosities again at a given filler content and styrene content, or which have higher styrene contents or solids contents at a given viscosity, than do the corresponding products produced with the conjoint use of other customary chain transfer agent/macromer combinations.
The present invention relates to a process for producing stable, low-viscosity graft copolymer dispersions which are free from agglomerates, by the radical polymerisation of ethylenically unsaturated monomers in a base polyol, char~rtrri~ed in that the polymerisation is effected in the presence of a polyol having ethylenically unsatuldled terminal groups (macromer) and of an enol ether of general formula A = CH-O-R
where A and R have the meaning given above, - - s -optionally in the presence of an organic solvent.
The process according to the invention is usually cond-lctP~ so that ethylenic~lly unsalul~led monomers, such as styrene and acrylonitrile for example, are reacted by S radical polymPri~tion~ in a polyalkylene oxide, which contains two to six hydroxyl groups and which has an OH number greater than 20, as the base polyol, in the presence of a polyol cont~ining ethylenically unsaturated groups (macromer) and an enol ether of the formula given above.
According to the invention, it is preferred that - the ethylenically unsaturated monomers are used in an amount of 25-65 % by weight with respect to the total amount of monomers and polyol, lS - mixtures of styrene and acrylonitrile are used as the ethylenically unsaturated monomers, - mixhres of styrene and acrylonitrile in a weight ratio of 20:80 to 100:0, most preferably 50:50 to 80:20, are used as the ethylenically unsaturated monomers, - a polyalkylene oxide containing at least two to six hydroxyl groups and with an O;~I number of 20 to 100, most preferably 30 to 70, is used as the base polycl, - the base polyol has a molecular weight of 1800 to 4500, most preferably 2000 to 4000 g/mole, - the polyol containing ethylenically unsaturated terminal groups (macromer) has a molecular weight of 3000 to 15,000, most preferably 4500 to 12,000 g/mole, and a functionality of 2-6, 2~ 71 ~&3 - the polyol con~ining ethylenically unsaturated terminal groups (macromer) contains a statistical average of 0.1-1.5, most preferably 0.3-1, moles of double bonds per mole of polyol, S - the polyol cont~ining ethylenically unsaturated te~ al groups (macromer) is used in an amount of 2 to 20, most preferably 3-10 % by weight with respect to the base polyol used, - (cyclohex-3-enylid~nPmçthoxymethyl)-benzene is used as the enol ether, - the enol ether is used in an amount of 0.1 to 5 % by weight with respect to the monomer mixture used, and - toluene or ethylbenzene is employed as the organic solvent which is optionally used in conjunction.
The present invention also relates to stable, low-viscosity graft copolymer dispersions which are free from agglomerates, which are obtainable by the process according to the invention, and to the use of the graft copolymer dispersions obtainable according to the invention as polyol components in the production of polyurethane foamed m~tçri~l~ by the isocyanate addition polymerisation process.
The polyols containing at least two hydroxyl groups which are used as the "base polyol" are preferably polyether polyols, e.g. the addition products known in the art of cyclic ethers such as ethylene oxide, propylene oxide, styrene oxide or butylene oxide with starter compounds, e.g. polyhydroxy compounds such as alkylene glycols, glycerine, trimethylolpropane, pentaerythritol, sorbitol, or amines such as ethylene-di~mine or toluylenedi~mine, for example. The polyether polyols used as the "base polyol" prefcrably have functionalities of 2 to 6 and an OH number of 20 to 100.The polyether chains are preferably built up from propylene oxide and ethylene oxide units. In principle, however, polyester polyols with functionalities of preferably 2 to 6 and an OH number of 20 to 100 can also be used as the "base polyolsN.
- 2 ~ 7 ~
The polymer polyols are obtained by the radical polym~ri~tion of ethylenically unsaturated monomers or ~I~ixl~l~s of ethylenically unsaturated monomers in the polyether polyols described above. Examples of monomers of this type include but~ienP, styrene, ~-methylstyrene, methylstyrene, ethylstyrene, acrylonitrile, meth~rrylonitrile, methyl meth~rrylate and acrylic acid esters. Styrene and acrylonitrile are preferably used. The amount of ethylenically unsatu,dted monomers is 25 to 65 % by weight, with respect to the total amount of final product. Whenusing styrene and acrylonitrile, the weight ratio of these two monomers is preferably 20:80 to 100:0, particularly 50:50 to 80:20 parts by weight.
Tniti~tion of the radical polymerisation is effected with the usual radical-forming initiators. Examples of initiators of this type include organic peroxides such as benzoyl peroxide, tert.-butyl octoate or dodecanoyl peroxide; or azo compounds such as azoisobutyronitrile or 2,2'-azobis(2-methylbutyronitrile).
The polyols used as the starting m~t~ri~l for the polyol cont~ining ethylenically unsaturated groups are likewise known polyether polyols such as the addition products known in the art of cyclic ethers such as ethylene oxide, propylene oxide, styrene oxide or butylene oxide with starter compounds, e.g. polyhydroxy compounds such as alkylene glycols, glycerine, trimethylolpropane, pentaerythritol or sorbitol, or amines such as ethylene~ mine or toluylPnedi~mine. The polyether polyols employed as the starting m~t~ri~l for the polyol containing ethylenically unsaturated groups have functionalities of 2 to 6 and a molecular weight of 3000 to 15,000 g/mole. The polyether chains are preferably built up from propylene oxide and ethylene oxideunits.
The ethylenically unsaturated groups may be introduced by methods known in the literature. Preferred methods include the reaction of the polyols with maleic anhydride and subsequent alkoxylation with ethylene- or propylene oxide, reaction with acrylic acid or the methyl or ethyl esters thereof, and reaction with an unsaturated isocyanate, such as 1-(1-isocyanato- 1-methylethyl)-3-(1-methylethenyl)-benzene or with an NCO-functional addition product of a polyisocyanate and hydroxyethyl- or hydroxypropyl acrylate, for example. Examples of polyisocyanates ~3 ~
which can be used for the preparation of the latter type include hPx~methylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and, most preferably, toluene diisocyanate.
The polyols cont~ining ethylenically unsaturated groups generally col~t~in~ as astati~tic~l average, 0.1 to 0.5, preferably 0.3-1 moles of double bonds per mole of polyol.
The enol ethers which are used conjointly according to the invention are known from the literature; their preparation is described, for example in German Auslegung.c~cllriften [Patents laid open to public inspectionl 1 668 091 and 1 768 396. Suitable repl~s~lltatives of this class of compounds are listed in EP 008 444, for example. (Cyclohex-3-enylidenemethoxymethyl)-benzene, which is commercially available under the trade name Vulkazon AFD from Bayer Ag, is particularly pleft;lled.
The enol ether is generally used in an amount of 0.1 to 5 % by weight with respect to the monomer mixture used.
Hydrocarbons such as toluene, ethylbenzene, isopropylbenzene or xylenes, ketonessuch as acetone or methyl ethyl ketone, or alcohols such as methanol, ethanol, isoplupanol or butanol may be employed as the solvent which is optionally used.
Toluene and ethylbenzene are preferred.
The process according to the invention may be conducted batch-wise or continuously.
For example, a mixture which contains an ethylenically unsaturated monomer, the enol ether, and optionally the solvent and part of the polyol to be used, may beintroduced into a stirred vessel which contains the preheated polyether and the macromer. However, it is also possible to add part of the macromer together withthe ethylenically unsaturated monomer, the enol ether, optionally the solvent and part of the polye'her. As a further possibility, the enol ether may also be placed in the reactor together with the polyether or with the major part of the polyether and the macromer and the rem~ining components may be added.
Further, a mixture of all the react~ntc may be continuously metered into a reactor and the product may be removed in the same amount via an overflow.
The te",peldture at which the polym~ri~tion is conducted is generally 80 to 140C, S preferably 9') to 130C.
When the polymeri~tion reaction is complete, the product is freed from readily volatile conctituent~ such as residual monomers, solvents, etc., by ~ till~tion under vacuum.
The polymer polyols produced by the process according to the invention are outstandingly suitable for the production of polyurethane plastics by the isocyanate addition polymeri~ation process. They are free from polymer agglomerates of any type, are stable and are of low viscosity. In this respect, it is particularly surprising 15 that the combination according to the invention of macromers with special enol ethers produces polymer polyols with an advantageously low viscosity when using low molecular weight base polyols with molecular weights between 1800 and 4500. Since the use of mercap~l chain extenders can be dispensed with in the process according to the invention, the products obtained are advantageously substantially odourless.
The production of polyurethane plastics, preferably of soft, flexible polyurethane foams, is effected by the reaction of a) organic polyisocyanates with 5 b) the polymer polyols according to the invention, optionally in the presence of c) other high molecular weight and/or low molecular weight compounds containing hydrogen atoms which react with isocyanates, d) catalysts, e) water and/or low-boiling hydrocarbons as foaming agents, and 2 ~ 3 f) auxiliary media and/or additives.
The following are used as starting components:
a) aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 362, pages 75 to 362, e.g. those of general formula Q(NCO)n where n ~e~resellls 2 to 5, preferably 2 and 3, and Q r~resents an aliphatic hydrocarbon radical cont~ining 2 to 18, preferably 6 to 10, carbon atoms, a cycloaliphatic hydrocarbon radical containing 4 to 15, preferably S to 10, carbon atoms, or an aromatic hydrocarbon radical cont~ining 6 to 15, preferably 6 to 13, carbon atoms, e.g. polyisocyanates such as those described in DE-OS 2 832 253, pages 10 to 11.
In general, polyisocyanates which are readily ~ccessible commercially are particularly p~feiied, e.g. toluene 2,4- and 2,6-diisocyanate and any mixtures of these isomers ("TDI"), diphenylmethane diisocyanate ("MDI") and polyphenylpolymethylene polyisocyanates such as those produced by the condensation of aniline with formaldehyde and subsequent phosgenation, and polyisocyanates cont~ininp carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or b.uret groups ("modified polyisocyanates), particularly those modifiedpolyisocyana~es which are derived from toluene 2,4- and/or 2,6-diisocyanate or from 4,4'- and/or 2,4'diphenylmethane isocyanate;
b) the polymer polyols according to the invention, ~1 7~
c) optionally, as starting materials, compounds cont~ining at least 2 hydrogen atoms which react with isocyanates and which have a molecular weight of 40 to 10,000 g/mole, preferably polyether polyols, i.e. addition products known in the art of cyclic ethers such as ethylene oxide, propylene oxide, styrene S oxide or butylene oxide with starter co~l~poullds, e.g. polyhydroxy compounds such as alkylene glycols, glycerine, trimethylolpropane, pentaerythritol, sorbi.ol, or amines such as ethylene~i~mine or toluylçnP~i~mine, as well as the starter compounds themselves;
d) according to the invention, the catalysts known in the art which are customary in polyurethane chemistry are optionally used in conjunction;
e) water and/or low-boiling hydrocarbons are optionally used in conjunction as foaming agents, e.g. low-boiling alkanes such as pentane, cyclo~lk~nes such as cyclopentane, and also alkenes, as well as gases such as carbon dioxide which are introduced under pressure into the reaction mixture;
f) ~uxili~ry agents and additives are optionally used in conjunction, such as fl) surface-active additives such as emulsifiers and foam stabilisers, f2) retarders, cell regulators of the type known in the art such as paraffins, fatty alcohols or dimethyl polysiloxanes, as well as pigm~nt~ or colorants and flame-retardants of the type known in the art, and also stabilisers against ageing and we~thering effects, softeners, and substances with fun~i~t~tic and bacteriostatic effects.
Examples of surface-active additives and foam stabilisers which may optionally be used in conjunction according to the invention, and of retarders, stabilisers, flame retardants, softeners, colorants, and substances with fungi~t~tic and bacteriostatic effects, and details of the mode of use and action of these substances, are described in the KunststQff-Handbuch [Plastics Handbook], Volume VII, edited by G. Oertel, Carl Hanser Verlag, Munich, 1993; e.g. on pages 104 to 127.
The flexible polyurell,al e foamed m~teri~l~ are produced in the manner known in the art, as described, for ex~mrle, in the K~lnst~toff-Handbook, Volume VII, edited by G. Oertel, Carl Hanser Verlag, Munich, 1993; e.g. on pages 139 to 263.
~i711~3 Examples:
Starting materials:
S polyol A: a polyether based on glycerine/propylene glycol (weight ratio 90: 10), prepared by the addition of PO (30 %), POtEO (40/10 %) and PO (20 %); OH No. = 56 mg KOH/g.
polyol B: a polyether of molecular weight 6000 based on trimethylolpropane, p~e~aled by the addition of PO (82.3 %) and EO (17.7 %).
polyol C: a polyether of molecular weight 4800 based on trimethylolpropane, prepared by the addition of PO (82.5 %) and EO (17.7 %).
polyol D: a polyether of molecular weight 3660 based on glycerine, ~l~alcd by the addition of PO (30 %), PO/EO (40/10 %) and PO (20 %); OH
No. = 46.
polyol E: a polyether of molecular weight 5430 based on trimethylolpropane, pl~paled by the addition of PO (17 %), PO/EO (51/17 %) and PO (15 %); OH No. = 31.
polymer polyol A: VP.PU 80WB40, from Bayer AG, solids content about 40 %, styrene content about 60 %.
macromer A the reaction product of one mole polyol C with 0.75 mole maleic anhydride, with the subsequent addition of 0.9 mole ethylene oxide.
The product had a double bond content of 49 meq/kg. 0 macromer B- the reaction product of one mole polyol C with 1.2 mole acrylic acid, prepa~ed by azeotropic esterification in the presence of 0.1 % by 2~ 71 ~ ~
weight p-toluenesulphonic acid (with respect to polyol C) and toluene as the solvent. The product had a double bond content of 100 meq/kg.
macromer C: the reaction product of one mole polyol B with 1.2 mole acrylic acid, prepared by azeolropic est~rific~tion in the presence of 0.1 % by weight p-toluçnesulI)honic acid (with respect to polyol D) and toluene as the solvent. The product had a double bond content of 139 meq/kg.
macromer D: the reaction product of one mole polyol C with the reaction product of 0.75 mole hydroxypropyl acrylate and 0.825 mole TDI. The product had a double bond content of 56 meq/kg.
macromer E: the reaction product of one mole polyol B with the reaction product of 0.75 mole hydroxypropyl acrylate and 0.9 mole TDI. The product had a double bond content of 71 meq/kg.
macromer F: the reaction product of one mole polyol C with one mole 1-(1-isocyanato- 1 -methylethyl)-3-( 1 -methylethenyl)-benzene. The product had a double bond content of 228 meq/kg. 0 macromer G: the reaction product of 1 mole polyol B with one mole l-(l-isocyanato-l-methylethyl)-3-(1-methylethenyl)-benzene. The product had a double bond content of 211 meq/kg.
enol ether A: (cyclohex-3-enylidenemethoxymethyl)-benzene (cis,trans-isomer mixture); commercial product of Bayer AG with the trade name Vulkazon AVD.
~O~
~ 7 ~
enol ether B: (cyclohex-3-enylidene)-cyclohexyl ether (cis,trans-isomer mixture), ~r~ared by the reaction of cyclohex-3-ene carbaldehyde with cyclohexanol in the presence of p-toluenesulphonic acid and quinoline, analogously to EP 008 444. b.p.: 82C/0.15 mbar.
~' ~l enol ether C: (norborn-3-enylidenemethoxymethyl)-benzene (cis,trans-isomer mixture), prepared by the reaction of 5-norbornene-2-aldehyde with benzyl alcohol in the presence of p-toluençsulphonic acid and quinoline, analogously to EP 008 444. b.p.: 106C/0.1 mbar (not according to the invention) ~0~
enol ether 1~: butylidene benzyl ether (cis,trans-isomer mixture), prepaled by the reaction of 2-butyraldehyde with benzyl alcohol in the presence of p-tol~çnesl-lphonic acid and quinoline, analogously to EP 008 444. b.p.:
73C/0.2 mbar (not according to the invention) ~o~[~
enol ether E (cyclohex-3-enylidene)-butylether (cis,trans-isomer mixture), prepared by the reaction of cyclohex-3-ene carbaldehyde with n-butanol in the presence of p-toluenes~llphonic acid and quinoline, analogously to EP
008 444. b.p.: 68C/0.1 mbar.
- ~1 7 ~
General specifications for the preparation of the polymer polyoLs:
A mixture concicting of 375.3 g polyol, 250.2 g styrene, 166.8 g acrylonitrile, 8.34 g enol ether ~or other chain transfer agent), 5.21 g 2,2'-azobis(2-methylbulyloilitrile) and 144 g toluene was added uniformly over 2 hours to a mixture of 225.2 g polyol and 25 g macromer, at 125C with stirring. The mixture was then stirred for a further 30 minutes at 125C. After continuously adding a solution of 0.92 g 2,2'-azobis(2-methylbutyronitrile) in 25.4 g toluene, the ~ ure was stirred for a further hour at 125C, and toluene and other volatile conctitllents were then listill~1 off at 125C, firstly for one hour under water pump vacuum (15 mbar), then for 2 hours under the vacuum from an oil pump (< 2 mbar). After cooling to about 100C, the product was passed through a sieve with a mesh size of 100 ~m.
Run-off test procedure:
About 3 ml polymer polyol were introduced into a 10 ml beaker with a curved rim,the inner walls of which were then completely wetted with polymer polyol by ch~king. After standing for 24 hours at room temperature, the residue rem~ining on the glass walls was ~csessed according to the number of particles of about 5-30 ~um diameter:
good: up to about 10 particles per cm2 average: from about 10 to 30 particles per cm2 poor: more than about 30 particles per cm2.
Examples 1-8:
Polymer polyols with polyol A as the base polyol and macromer A as the macromer were pre~alc;d according to the general preparation specificahion; different chain S h-ansfer agents were used. The reachon was also conducte~1 without a chain hansfer agent, for comparison.
The results are sllmm~ ed in the following Table:
Example Chain hransfer agent viscosity Run-off (mPa. s/25 C) --- 3990 good 2 isopropanol 3760 [1] poor 3 2-butanol 3710 good 4 methyl ethyl ketone 3720 good tehachloromethane 3740 good 6 l-dodecylme~a~l 4990 average 7 enol ether A 3240 good 8 enol ether B 3190 good [1] unfilterable product In this series, enol ethers A and B according to the invenhon gave the lowest vlscosihes.
Examples 9-19:
Polymer polyols with polyol A as the base polyol and macromer B as the macromer were ~epaled according to the general preparation spe~ific~tion; dirre~ t chain S transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
The results are sl-mm~ri~ed in the following Table:
Example Chain transfer agentviscosity Run-off (mPa.s/25C) t2]
isop~opaulol 7450 [1] poor 11 2-butanol 7970 [1] poor 12 methyl ethyl ketone --- [3] ---13 tetrachloromethane 4000 good 14 l-dodecylmerca~tall 29850 poor enol ether A 3550 good 16 enol ether B 3450 good 17 enol ether C --- [3] ---18 enol ether D 4480 average 19 enol ether E 3480 good [1] unfil~erable product [2] the reaction had to be terminated because the batch could no longer be stirred due to its viscosity being too high [3] caked; the reaction had to be termin~ted In this series, enol ethers A, B and E according to the invention gave finely divided, low-viscosity products, whilst enol ethers C and D, which were not according to the Le A 30 960 - 01 ~ 7 ~
invention, and the other chain transfer agents gave dispersions which were unstable or which contained coarse particles and had higher vi~co~iti~.
Examples 2n-27:
s Polymer polyols with polyol A as the base polyol and macromer C as the macromer were pr~ared according to the general preparation specification; different chain transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
The results are summarised in the following Table:
Example Chain transfer agentviscosity Run-off (mPa.s/25C) --~ 4950 tl] poor 21 isopropanol 4330 [1] poor 22 2-butanol 4710 [1] poor 23 methyl ethyl ketone 4630 poor 24 tetrachloromethane 4100 average l-dodecylmercaptan --- [2] ---26 enol ether A 3550 good 27 enol ether B 3300 good [1] unfilterable product [2] the reaction had to be termin~t~d because the batch could no longer be stirred due to its viscosity being too high Enol ethers A and B according to the invention also gave finely divided, low-viscosity products in combination with macromer C, whilst the other chain transfer agents gave dispersions which were unstable or which contained coarse particles and had higher viscosities.
Examples 28-35:
Polymer polyols with polyol A as the base polyol and macromer D as the macromer were ~,epa~ed according to the general pr~al~lion spet~ific~tion; different chain transfer agents were used. The reaction was also cQ~ cted without a chain transfer agent, for comparison.
The results are summ~ri~ed in the following Table:
Example Chain transfer agentviscosity Run-off (mPa.s/25C) 28 --- 19000 [1] poor 29 isopropanol --- t3] ---2-butanol --- [2] ---31 methyl ethyl ketone --- [3] ---32 tetrachlorometh~ne 5840 average 33 l-dodecylme~a~tan 13200 poor 34 enol ether A 3140 good enol ether B 3340 good [1] unfilt~srable product [2] the reaction had to be termin~ted because the batch could no longer be stirred due to its viscosity being too high [3] cakec; the reaction had to be termin~ted.
In combination with macromer D, the advantage of enol ethers A and B according to the invention becomes even clearer. Stable, low-viscosity products were only obtained with the latter.
Examples 3~43:
Polymer polyols with polyol A as the base polyol and macromer E as the macromer were plepaled according to the general preparation specification; different chain transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
The results are summarised in the following Table:
Example Chain transfer agent viscosity Run-off (mPa. s/25 C) 36 7110 [1] poor 37 isopropanol 4800 [1] poor 38 2-butanol 5180 poor 39 methyl ethyl ketone 5100 poor tetrachloromethane 4850 average 41 1 -dodecylmercap~l 5250 average 42 enol ether A 3550 good 43 enol ether B 3260 good [1] unfilterable product Only enol ethers A and B according to the invention gave finely divided, low-viscosity products.
Examples 44-51:
Polymer polyols with polyol A as the base polyol and macromer F as the macromer were prepared according to the general preparation specification; different chain transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
~7 1~ ~3 The results are summarised in the following Table:
Example Chain transfer agent viscosity Run-off (mPa.s/25C) 44 --- [2]
isopropanol --- [2] ---46 2-butanol --- [2] ---47 methyl ethyl ketone --- [2] ---48 tetrachloromethane 6410 poor 49 l-dodecylmercaptan 5870 poor enol ether A 4410 good 51 enol ether B 4020 good [2] the reaction had to be termin~ted because the batch could no longer be stirred due to its viscosity being too high In combination with macromer F, the advantage of enol ethers A and B according to the inventior. becomes particularly clear. Only the latter gave finely divided, low-viscosity dispersions. Dispersions which were either unstable or which containedcoarse particles and had high viscosities were obtained with the chain transfer agents which were not according to the invention.
Examples 5''-59:
Polymer polyols with polyol A as the base polyol and macromer G as the macromer were prepared according to the general preparation specification; different chain transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
The results are summ~riced in the following Table:
~:~ 7 ~
Example Chain transfer agent viscosity Run-off (mPa.s/25 oc) 52 --- 9500 poor 53 isopr~anol 6800 [1] poor 54 2-butanol 6330 poor methyl ethyl ketone 5950 poor 56 tetrachlorome~h~ne 4940 average 57 l-dodecylmercaptan 3800 average 58 enol ether A 3480 good 59 enol ether B 3780 good [1] unfilterable product Only enol ethers A and B according to the invention gave finely divided, low-viscosity products.
Examples 6t)-91:
Use of the polymer polyols according to the invention, from Examples 8, 15, 27, 35, 42, 50 and 59, for the production of flexible foamed materials:
To produce a laboratory foam, all the components - apart from catalyst 3 and thepolyisocyanate - were intensively mixed with each other. Thereafter, catalyst 3 was added, mixed for a short period, and the polyisocyanate was then added with stirring.
The reaction mixture was subsequently poured into an open mould, in which it foamed to form the flexible foam.
The results of the foam tests are summ~n~ed in the following Tables (all amounts in parts by weight).
Catalyst 1: Desmorapid0 DMEA, manufactured by Rhein Chemie, Rheinau Catalyst 2: RC-PUR activator 108, manufactured by Rhein Chelnie, Rheinau Catalyst 3: Desmorapid~ SO, manufactured by Rhein Chemie, Rheinau Stabiliser: Stabiliser OS 22, manufactured by Bayer AG
Isocyanate: toluene diisocyanate (Desmodur'~9 T 80, Bayer AG) Results of foam formulation with a 10 æ filler content (data in % by weight, characteristic number 108, a~arent density about 23 to 24 kg/n~
Ex. 60 Ex. 61 Ex. 62 Ex. 63 Ex. 64 E~. 65 E1~. 66 E~. 67 Polyol A 75 75 75 75 75 75 75 75 Polymer polyol A 25 Example 8 25 E~cample 15 25 Example 27 25 Example 35 25 Example 42 25 Example 50 25 Example 59 25 Water 4 5 4 5 4 5 4 5 4 5 4-Stabiliser Catalyst 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Catalyst 3 0.13 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Foaming capacity very good very good very good very good very good very good very good very good Open cellularity very good very good very good very good very good very good very good very good Apparent density according to DIN 53 420 (kg/m3) 23 24 24 23 24 24 24 24 Tensile strength ~ rd;l,g to DIN 53 571 (kPa) 121 126 126 145 137 123 146 128 Breaking elongation acco,d;.,g to DIN 53 571 (%) 131 103 117 128 123 97 125 101 40 % Strain hardness according to DIN 53 577 (kPa) 4.4 5.5 4.9 5.1 5.3 5.6 5.4 5.7 Grip/elasti.;il~ very good very good very good very good very good very good very good very good Results of foam formulation with a 20 % filler content (data in % by weight, chd,~ctelistic number 108, apparent density about 23 to 24 kg/m3 Ex. 68 Ex. 69 E~c. 70 Ex. 71 E~c. 72 E~c. 73 Ex. 74 E~. 75 Polyol A 50 50 50 50 50 50 50 50 Polymer polyol A 50 Example 8 50 Example 15 50 Example 27 50 Example 35 50 Example 42 50 Example 50 50 Example 59 50 Water 4 5 4 5 4 5 4 5 4 5 Stabiliser Catalyst 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Catalyst 3 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 Foaming capacity very good very good very good very good very good very good very good very good Open cellularity very good very good very good very good very good very good very good very good Apparent density according to DIN 53 420 (kg/m3) 23 23 23 23 23 24 23 23 Tensile strength dccoldillg to DIN 53 571 (kPa) 147 121 148 144 148 144 137 141 Breaking elongationaccording to DIN 53 571 (%) 126 95 97 86 100 102 103 108 40 % Strain hardness accor.ling to DIN 53 577 (kPa) 5.7 6.1 6.1 6.8 6 6.1 5.9 5.6 Grip/el~t;~,;t~ very good very good very good very good very good very good very good very good Results of foam formulation with a 10 % filler content (data in % by weight, chal~t.,.i~lic number 108, apparent density about 37 to 39 kg/m3 Ex. 76 Ex. 77 E~c. 78 E~c. 79 Ex. 80 Ex. 81 Ex. 82 E~t. 83 Polyol A 75 75 75 75 75 75 75 75 Polymer polyol A 25 Example 8 25 Example 15 25 Example 27 25 Example 35 25 Example 42 25 Example 50 25 Example 59 25 Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stabiliser 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Catalyst 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Catalyst 3 0.13 0.12 0.12 0.12 0.12 0.12 0.12 0.12 Foaming capacity very good very good very good very good very good very good very good very good Open cellularity very good very good very good very good very good very good very good very good Apparent density according to DIN 53 420 (kg/m3) 37 38 38 38 38 39 38 38 Tensile strength r-~c .lillg to DIN 53 571 (kPa) 156 142 104 160 149 147 157 146 Breaking elongation accol.l;ng to DIN 53 57l (%) 155 142 114 156 141 138 145 148 j, 40 9to Strain hardness according to DIN 53 577 (kPa) 5.6 5.2 5 5.3 5.4 5.3 5.5 5.4 Grip/cla~ very good very good very good very good very good vely good very good very good Results of foam formulation with a 20 % filler content (data in % by weight, cLa.~ leristic number 108, apparent density about 37 to 39 kg/m3 F.x. 84 Ex. 85 Ex. 86 Ex. 87 Ex. 88 Ex. 89 E~c. 90 E~. 91 Polyol A 50 50 50 50 50 50 50 50 Polymer polyol A 50 Example 8 50 Example 15 50 Example 27 50 Example 35 50 Example 42 50 Example 50 5 Example 59 Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stabiliser 0.7 0.7 0.7 0.7 07 0 7 07 0 7 Catalyst 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Catalyst 3 0.13 0.12 0.12 0.12 0.12 0.12 0.12 0.12 Foaming capacity very good very good very good very good very good very good very good very good Open cellularity very good very good very good very good very good very good very good very good Apparent density acco.dh~g to DIN 53 420 (kg/m3) 36 38 38 37 38 39 37 39 Tensile strength acco.. li.. g to DIN 53 571 (kPa) 182 159 187 195 181 162 166 173 Breaking el~-nga~ion according to DIN 53 571 (%) 148 109 131 146 131 108 121 110 40 % Strain hardness according to DIN 53 577 (kPa) 6.4 6.9 6.6 6.6 6.8 6.8 6.6 7 Grip/elasticity very good very good very good very good very good very good very good very good Foaming examples 60 - 91 show that the finely divided, low-viscosity polymer polyol dispersions according to the invention result in foams, the propel~ies of which are col.-pa,~ble with current commercial products of higher viscosity. On account of their lower viscosity at a given filler content, foam formulations based on the products according to the invention can be processed more easily. Moreover, higher solidscontents, which result in foams of correspondingly greater hardness, can be obtained with them, taking an identical maximum processing viscosity into consideration.
Comparative Examples 1 to 6:
For comparison purposes, polymer polyols were prepared in the presence of enol ethers without the addition of macromer.
A mixture conci~ting of 375.3 g polyol, 250 g styrene, 166.8 g acrylonitrile, 8.34 g enol ether A, 5.2 g 2,2'-azobis(2-methyl-butyronitrile) and 144 g toluene was added uniformly over 2 hours to 250.2 g of polyol, with stirring, in a nitrogen atmosphere at 125C. The mixture was stirred for a further 30 minutes at 125C. After the continuous addition of a solution of 0.9 g 2,2'-azobis(2-methyl-butyronitrile) in 25.4 g toluene, stirring was continued for a further hour at 125C, and then toluene and other volatile concti~lents were distilled off at 125C, firstly for one hour under the vacuum from a water pump (15 mbar) and then for 2 hours undel the vacuum from an oil pump (< 2 mbar). After cooling to about 100C, the product was passed through a sieve of mesh aperture 100 ~m.
The results of the comparative tests are summarised in the following Table.
Comparison Polyol Enol Viscosity Progress Example ether (MPas/25C) Polyol A - caked [1]
2 Polyol A Vulkazon caked [1]
AFD
3 Polyol D
4 Polyol D Vulka~on highly [2]
AFD viscous Polyol E - 21,780 poor 6 Polyol E Vulkazon 7180 poor AFD
[1] dispersion unstable; reaction had to be stopped [2] the reaction mixture was so viscous that the reaction had to be stopped The comparative tests show that only undesirably highly viscous or caked polymer polyols are obtained without the addition of macromers.
PE/AB/S-P
Low-~ is~o~ polymer polyols, a ~l oce~ for pro~ r;n~ them. and their use for the production of polyul~ll,ane foamed materials Within the scope of the present invention, polymer polyols are understood to be products which can be obtained by the polymeric~tion of ethylenically unsaturated compounds in polyether polyols ("base polyols"). These can be used for the production of flexible polyurethane foamed m~tt-ri~l~, for example. The ethyleni-~lly unsaturated compounds which are mainly used are the monomers styrene and acrylonitrile, which may be radically polymP-ri~ed in polyether polyols as the base polyol.
The production of polymer polyols such as these is described in US Patent Specifications 3 383 351 and 3 304 273 and in DE-A 1 152 536 and DE-A 1 152 537, for example.
In the ideal case, polymer polyols are relatively low-viscosity, finely divided non-se-iimenting dispersions of the nolymer (preferably an acrylonitrile/styrene graft copolymer) in the substantially unchanged polyether polyol. The characterising features for the quality and processability of polymer polyols are their viscosity, storage stability (resistance to se~imPnt~tinn) and finely divided state. These properties are mainly influenced by the type and q~l~ntit~tive ratios of the starting m~teri~ls. In particular, the solids content (proportion of monomer in the batch) and the monomer ratio (e.g. the styrene/acrylonitrile ratio) have a considerable effect on product quality.
The most important targets when producing polymer polyols are the ~tt~inment of high solids contents (at least 40 %), with a styrene content which is as high aspossible and a viscosity which is as low as possible, and with excellent productstability at the same time.
In order to attain product stability, i.e. the suppression of unwanted agglomerated polymer particles precipitated from the continuous phase, i.e. from the base polyol, the polymer particles have to be stabilised during the production of the polymerpolyol. This stabilisation is first of all effected by the incorporation of part of the molecule of ~he base polyether in the polymer formed in situ. In this connection, the efficacy of stabilisation is firstly e.nh~n~ e~ by a molecular weight of the base polymer which is as high as possible and by the highest possible content of acrylonitrile in the monomer mixture. Whereas a high acrylonitrile content increases the intrin~ic colour of polymer polyols and the tendency towards discoloration of flexible foams produced with them, and is thus undesirable, the viscosity of polymer polyols is increased by the use of base polyols of higher molecular weights.
One possible way of obtaining low-viscosity polymer polyols having a high content of filler m~t-~ri~l~, which is subst~nti~lly independent of the molecular weight of the base polyol, is to use chain extenders in conjunction. Examples of the latter for this application include the merca~ls, halogen alkanes or alcohols which are customary in polymerisation technology.
Moreover, the use in conjunction of enol ethers as chain transfer agents is described in EP-A 008 444, due to which it is claimed to be possible to produce polymer polyols having a relatively low viscosity at a relatively high filler content and styrene content.
Another possible way of stabilising polymer polyols is the use in conjunction ofcompounds which are compatible with the polyol phase and which contain ethylenically unsaturated groups which are capable of polymerisation. These so-called macromers copolymerise with the vinyl monomers, so that the polymer particles produced are steric~lly stabilised by polyether side chains and are thus protected from agglomeration and sedimentation.
The production of polymer polyols with the use in conjunction of macromers is described in US-PS 3 652 639, US-PS 3 823 201, US-PS 4 460 715, US-PS 4 390 645, US-PS 5 093 412 and US-PS 4 342 840, for example. The ethylenically ~ 7~ ~3 unsaturated double bonds are introduced into polyether polyols, for example, by reaction with cyclic, unsaturated carboxylic acid anhydrides such as maleic anhydride and subsequent reaction with ethylene- or propylene oxide; by est~nfi~tion with acrylic or mçth~crylic acid (derivatives); by reaction with allyl glycidyl ethers; by S reaction with an unsdLul~ted isocyanate, such as an isocy~n~to~lkyl acrylate and m~th~rylate or 1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)-benæne, for example, or NCO-functional addition compounds of a polyisocyanate and hydroxyethyl or hydroxypropyl acrylate, for example.
The combination of macromers with chain transfer agents such as mercaptans or alcohols has also already been described in DE-A-2 500 274, EP-A-019 769, and inEP-A 0 091 036. Products produced using me,~ tans have the disadvantage that they mostly have an odour which is unpleasant to a greater or lesser extent.
Moreover, products such as these often do not have the desired viscosity.
Even when the aforementioned processes lead to polymer polyols which can be usedin principle as polyol components for the production of polyurethane flexible foams, further improvements are still desirable. Thus the vi~cosities taken from the literature of highly filled polymer polyols are always still quite high, particularly at high styrene contents in the monomer mixture, and smaller, agglomerated polymer particles are often observed in the run-off, i.e. the products are not sufficiently finely divided.
It has now surprisingly been found that polymer polyols which are free from agglomerates and which have high filler contents and low viscosities can be produced by producing the polymer polyols in the presence of a macromer of the type described above and an enol ether of general formula A=CH-O-R
where 2 ~a 7 1 I ~ ~
A is a divalent radical of formula R~ ~
R ,~resents a C, l8 alkyl, C5 ,0 cycloalkyl or optionally a benzyl radical with a substituted nucleus, and R' represents hydrogen or a C, 8 alkyl radical.
By the use in conjunction of a combination of macromers with special chain transfer agents of the enol ether type as described above, stable, finely divided polymerpolyols become ~ccçs~ible, as shown in the comparative examples, which have lower viscosities again at a given filler content and styrene content, or which have higher styrene contents or solids contents at a given viscosity, than do the corresponding products produced with the conjoint use of other customary chain transfer agent/macromer combinations.
The present invention relates to a process for producing stable, low-viscosity graft copolymer dispersions which are free from agglomerates, by the radical polymerisation of ethylenically unsaturated monomers in a base polyol, char~rtrri~ed in that the polymerisation is effected in the presence of a polyol having ethylenically unsatuldled terminal groups (macromer) and of an enol ether of general formula A = CH-O-R
where A and R have the meaning given above, - - s -optionally in the presence of an organic solvent.
The process according to the invention is usually cond-lctP~ so that ethylenic~lly unsalul~led monomers, such as styrene and acrylonitrile for example, are reacted by S radical polymPri~tion~ in a polyalkylene oxide, which contains two to six hydroxyl groups and which has an OH number greater than 20, as the base polyol, in the presence of a polyol cont~ining ethylenically unsaturated groups (macromer) and an enol ether of the formula given above.
According to the invention, it is preferred that - the ethylenically unsaturated monomers are used in an amount of 25-65 % by weight with respect to the total amount of monomers and polyol, lS - mixtures of styrene and acrylonitrile are used as the ethylenically unsaturated monomers, - mixhres of styrene and acrylonitrile in a weight ratio of 20:80 to 100:0, most preferably 50:50 to 80:20, are used as the ethylenically unsaturated monomers, - a polyalkylene oxide containing at least two to six hydroxyl groups and with an O;~I number of 20 to 100, most preferably 30 to 70, is used as the base polycl, - the base polyol has a molecular weight of 1800 to 4500, most preferably 2000 to 4000 g/mole, - the polyol containing ethylenically unsaturated terminal groups (macromer) has a molecular weight of 3000 to 15,000, most preferably 4500 to 12,000 g/mole, and a functionality of 2-6, 2~ 71 ~&3 - the polyol con~ining ethylenically unsaturated terminal groups (macromer) contains a statistical average of 0.1-1.5, most preferably 0.3-1, moles of double bonds per mole of polyol, S - the polyol cont~ining ethylenically unsaturated te~ al groups (macromer) is used in an amount of 2 to 20, most preferably 3-10 % by weight with respect to the base polyol used, - (cyclohex-3-enylid~nPmçthoxymethyl)-benzene is used as the enol ether, - the enol ether is used in an amount of 0.1 to 5 % by weight with respect to the monomer mixture used, and - toluene or ethylbenzene is employed as the organic solvent which is optionally used in conjunction.
The present invention also relates to stable, low-viscosity graft copolymer dispersions which are free from agglomerates, which are obtainable by the process according to the invention, and to the use of the graft copolymer dispersions obtainable according to the invention as polyol components in the production of polyurethane foamed m~tçri~l~ by the isocyanate addition polymerisation process.
The polyols containing at least two hydroxyl groups which are used as the "base polyol" are preferably polyether polyols, e.g. the addition products known in the art of cyclic ethers such as ethylene oxide, propylene oxide, styrene oxide or butylene oxide with starter compounds, e.g. polyhydroxy compounds such as alkylene glycols, glycerine, trimethylolpropane, pentaerythritol, sorbitol, or amines such as ethylene-di~mine or toluylenedi~mine, for example. The polyether polyols used as the "base polyol" prefcrably have functionalities of 2 to 6 and an OH number of 20 to 100.The polyether chains are preferably built up from propylene oxide and ethylene oxide units. In principle, however, polyester polyols with functionalities of preferably 2 to 6 and an OH number of 20 to 100 can also be used as the "base polyolsN.
- 2 ~ 7 ~
The polymer polyols are obtained by the radical polym~ri~tion of ethylenically unsaturated monomers or ~I~ixl~l~s of ethylenically unsaturated monomers in the polyether polyols described above. Examples of monomers of this type include but~ienP, styrene, ~-methylstyrene, methylstyrene, ethylstyrene, acrylonitrile, meth~rrylonitrile, methyl meth~rrylate and acrylic acid esters. Styrene and acrylonitrile are preferably used. The amount of ethylenically unsatu,dted monomers is 25 to 65 % by weight, with respect to the total amount of final product. Whenusing styrene and acrylonitrile, the weight ratio of these two monomers is preferably 20:80 to 100:0, particularly 50:50 to 80:20 parts by weight.
Tniti~tion of the radical polymerisation is effected with the usual radical-forming initiators. Examples of initiators of this type include organic peroxides such as benzoyl peroxide, tert.-butyl octoate or dodecanoyl peroxide; or azo compounds such as azoisobutyronitrile or 2,2'-azobis(2-methylbutyronitrile).
The polyols used as the starting m~t~ri~l for the polyol cont~ining ethylenically unsaturated groups are likewise known polyether polyols such as the addition products known in the art of cyclic ethers such as ethylene oxide, propylene oxide, styrene oxide or butylene oxide with starter compounds, e.g. polyhydroxy compounds such as alkylene glycols, glycerine, trimethylolpropane, pentaerythritol or sorbitol, or amines such as ethylene~ mine or toluylPnedi~mine. The polyether polyols employed as the starting m~t~ri~l for the polyol containing ethylenically unsaturated groups have functionalities of 2 to 6 and a molecular weight of 3000 to 15,000 g/mole. The polyether chains are preferably built up from propylene oxide and ethylene oxideunits.
The ethylenically unsaturated groups may be introduced by methods known in the literature. Preferred methods include the reaction of the polyols with maleic anhydride and subsequent alkoxylation with ethylene- or propylene oxide, reaction with acrylic acid or the methyl or ethyl esters thereof, and reaction with an unsaturated isocyanate, such as 1-(1-isocyanato- 1-methylethyl)-3-(1-methylethenyl)-benzene or with an NCO-functional addition product of a polyisocyanate and hydroxyethyl- or hydroxypropyl acrylate, for example. Examples of polyisocyanates ~3 ~
which can be used for the preparation of the latter type include hPx~methylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and, most preferably, toluene diisocyanate.
The polyols cont~ining ethylenically unsaturated groups generally col~t~in~ as astati~tic~l average, 0.1 to 0.5, preferably 0.3-1 moles of double bonds per mole of polyol.
The enol ethers which are used conjointly according to the invention are known from the literature; their preparation is described, for example in German Auslegung.c~cllriften [Patents laid open to public inspectionl 1 668 091 and 1 768 396. Suitable repl~s~lltatives of this class of compounds are listed in EP 008 444, for example. (Cyclohex-3-enylidenemethoxymethyl)-benzene, which is commercially available under the trade name Vulkazon AFD from Bayer Ag, is particularly pleft;lled.
The enol ether is generally used in an amount of 0.1 to 5 % by weight with respect to the monomer mixture used.
Hydrocarbons such as toluene, ethylbenzene, isopropylbenzene or xylenes, ketonessuch as acetone or methyl ethyl ketone, or alcohols such as methanol, ethanol, isoplupanol or butanol may be employed as the solvent which is optionally used.
Toluene and ethylbenzene are preferred.
The process according to the invention may be conducted batch-wise or continuously.
For example, a mixture which contains an ethylenically unsaturated monomer, the enol ether, and optionally the solvent and part of the polyol to be used, may beintroduced into a stirred vessel which contains the preheated polyether and the macromer. However, it is also possible to add part of the macromer together withthe ethylenically unsaturated monomer, the enol ether, optionally the solvent and part of the polye'her. As a further possibility, the enol ether may also be placed in the reactor together with the polyether or with the major part of the polyether and the macromer and the rem~ining components may be added.
Further, a mixture of all the react~ntc may be continuously metered into a reactor and the product may be removed in the same amount via an overflow.
The te",peldture at which the polym~ri~tion is conducted is generally 80 to 140C, S preferably 9') to 130C.
When the polymeri~tion reaction is complete, the product is freed from readily volatile conctituent~ such as residual monomers, solvents, etc., by ~ till~tion under vacuum.
The polymer polyols produced by the process according to the invention are outstandingly suitable for the production of polyurethane plastics by the isocyanate addition polymeri~ation process. They are free from polymer agglomerates of any type, are stable and are of low viscosity. In this respect, it is particularly surprising 15 that the combination according to the invention of macromers with special enol ethers produces polymer polyols with an advantageously low viscosity when using low molecular weight base polyols with molecular weights between 1800 and 4500. Since the use of mercap~l chain extenders can be dispensed with in the process according to the invention, the products obtained are advantageously substantially odourless.
The production of polyurethane plastics, preferably of soft, flexible polyurethane foams, is effected by the reaction of a) organic polyisocyanates with 5 b) the polymer polyols according to the invention, optionally in the presence of c) other high molecular weight and/or low molecular weight compounds containing hydrogen atoms which react with isocyanates, d) catalysts, e) water and/or low-boiling hydrocarbons as foaming agents, and 2 ~ 3 f) auxiliary media and/or additives.
The following are used as starting components:
a) aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 362, pages 75 to 362, e.g. those of general formula Q(NCO)n where n ~e~resellls 2 to 5, preferably 2 and 3, and Q r~resents an aliphatic hydrocarbon radical cont~ining 2 to 18, preferably 6 to 10, carbon atoms, a cycloaliphatic hydrocarbon radical containing 4 to 15, preferably S to 10, carbon atoms, or an aromatic hydrocarbon radical cont~ining 6 to 15, preferably 6 to 13, carbon atoms, e.g. polyisocyanates such as those described in DE-OS 2 832 253, pages 10 to 11.
In general, polyisocyanates which are readily ~ccessible commercially are particularly p~feiied, e.g. toluene 2,4- and 2,6-diisocyanate and any mixtures of these isomers ("TDI"), diphenylmethane diisocyanate ("MDI") and polyphenylpolymethylene polyisocyanates such as those produced by the condensation of aniline with formaldehyde and subsequent phosgenation, and polyisocyanates cont~ininp carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or b.uret groups ("modified polyisocyanates), particularly those modifiedpolyisocyana~es which are derived from toluene 2,4- and/or 2,6-diisocyanate or from 4,4'- and/or 2,4'diphenylmethane isocyanate;
b) the polymer polyols according to the invention, ~1 7~
c) optionally, as starting materials, compounds cont~ining at least 2 hydrogen atoms which react with isocyanates and which have a molecular weight of 40 to 10,000 g/mole, preferably polyether polyols, i.e. addition products known in the art of cyclic ethers such as ethylene oxide, propylene oxide, styrene S oxide or butylene oxide with starter co~l~poullds, e.g. polyhydroxy compounds such as alkylene glycols, glycerine, trimethylolpropane, pentaerythritol, sorbi.ol, or amines such as ethylene~i~mine or toluylçnP~i~mine, as well as the starter compounds themselves;
d) according to the invention, the catalysts known in the art which are customary in polyurethane chemistry are optionally used in conjunction;
e) water and/or low-boiling hydrocarbons are optionally used in conjunction as foaming agents, e.g. low-boiling alkanes such as pentane, cyclo~lk~nes such as cyclopentane, and also alkenes, as well as gases such as carbon dioxide which are introduced under pressure into the reaction mixture;
f) ~uxili~ry agents and additives are optionally used in conjunction, such as fl) surface-active additives such as emulsifiers and foam stabilisers, f2) retarders, cell regulators of the type known in the art such as paraffins, fatty alcohols or dimethyl polysiloxanes, as well as pigm~nt~ or colorants and flame-retardants of the type known in the art, and also stabilisers against ageing and we~thering effects, softeners, and substances with fun~i~t~tic and bacteriostatic effects.
Examples of surface-active additives and foam stabilisers which may optionally be used in conjunction according to the invention, and of retarders, stabilisers, flame retardants, softeners, colorants, and substances with fungi~t~tic and bacteriostatic effects, and details of the mode of use and action of these substances, are described in the KunststQff-Handbuch [Plastics Handbook], Volume VII, edited by G. Oertel, Carl Hanser Verlag, Munich, 1993; e.g. on pages 104 to 127.
The flexible polyurell,al e foamed m~teri~l~ are produced in the manner known in the art, as described, for ex~mrle, in the K~lnst~toff-Handbook, Volume VII, edited by G. Oertel, Carl Hanser Verlag, Munich, 1993; e.g. on pages 139 to 263.
~i711~3 Examples:
Starting materials:
S polyol A: a polyether based on glycerine/propylene glycol (weight ratio 90: 10), prepared by the addition of PO (30 %), POtEO (40/10 %) and PO (20 %); OH No. = 56 mg KOH/g.
polyol B: a polyether of molecular weight 6000 based on trimethylolpropane, p~e~aled by the addition of PO (82.3 %) and EO (17.7 %).
polyol C: a polyether of molecular weight 4800 based on trimethylolpropane, prepared by the addition of PO (82.5 %) and EO (17.7 %).
polyol D: a polyether of molecular weight 3660 based on glycerine, ~l~alcd by the addition of PO (30 %), PO/EO (40/10 %) and PO (20 %); OH
No. = 46.
polyol E: a polyether of molecular weight 5430 based on trimethylolpropane, pl~paled by the addition of PO (17 %), PO/EO (51/17 %) and PO (15 %); OH No. = 31.
polymer polyol A: VP.PU 80WB40, from Bayer AG, solids content about 40 %, styrene content about 60 %.
macromer A the reaction product of one mole polyol C with 0.75 mole maleic anhydride, with the subsequent addition of 0.9 mole ethylene oxide.
The product had a double bond content of 49 meq/kg. 0 macromer B- the reaction product of one mole polyol C with 1.2 mole acrylic acid, prepa~ed by azeotropic esterification in the presence of 0.1 % by 2~ 71 ~ ~
weight p-toluenesulphonic acid (with respect to polyol C) and toluene as the solvent. The product had a double bond content of 100 meq/kg.
macromer C: the reaction product of one mole polyol B with 1.2 mole acrylic acid, prepared by azeolropic est~rific~tion in the presence of 0.1 % by weight p-toluçnesulI)honic acid (with respect to polyol D) and toluene as the solvent. The product had a double bond content of 139 meq/kg.
macromer D: the reaction product of one mole polyol C with the reaction product of 0.75 mole hydroxypropyl acrylate and 0.825 mole TDI. The product had a double bond content of 56 meq/kg.
macromer E: the reaction product of one mole polyol B with the reaction product of 0.75 mole hydroxypropyl acrylate and 0.9 mole TDI. The product had a double bond content of 71 meq/kg.
macromer F: the reaction product of one mole polyol C with one mole 1-(1-isocyanato- 1 -methylethyl)-3-( 1 -methylethenyl)-benzene. The product had a double bond content of 228 meq/kg. 0 macromer G: the reaction product of 1 mole polyol B with one mole l-(l-isocyanato-l-methylethyl)-3-(1-methylethenyl)-benzene. The product had a double bond content of 211 meq/kg.
enol ether A: (cyclohex-3-enylidenemethoxymethyl)-benzene (cis,trans-isomer mixture); commercial product of Bayer AG with the trade name Vulkazon AVD.
~O~
~ 7 ~
enol ether B: (cyclohex-3-enylidene)-cyclohexyl ether (cis,trans-isomer mixture), ~r~ared by the reaction of cyclohex-3-ene carbaldehyde with cyclohexanol in the presence of p-toluenesulphonic acid and quinoline, analogously to EP 008 444. b.p.: 82C/0.15 mbar.
~' ~l enol ether C: (norborn-3-enylidenemethoxymethyl)-benzene (cis,trans-isomer mixture), prepared by the reaction of 5-norbornene-2-aldehyde with benzyl alcohol in the presence of p-toluençsulphonic acid and quinoline, analogously to EP 008 444. b.p.: 106C/0.1 mbar (not according to the invention) ~0~
enol ether 1~: butylidene benzyl ether (cis,trans-isomer mixture), prepaled by the reaction of 2-butyraldehyde with benzyl alcohol in the presence of p-tol~çnesl-lphonic acid and quinoline, analogously to EP 008 444. b.p.:
73C/0.2 mbar (not according to the invention) ~o~[~
enol ether E (cyclohex-3-enylidene)-butylether (cis,trans-isomer mixture), prepared by the reaction of cyclohex-3-ene carbaldehyde with n-butanol in the presence of p-toluenes~llphonic acid and quinoline, analogously to EP
008 444. b.p.: 68C/0.1 mbar.
- ~1 7 ~
General specifications for the preparation of the polymer polyoLs:
A mixture concicting of 375.3 g polyol, 250.2 g styrene, 166.8 g acrylonitrile, 8.34 g enol ether ~or other chain transfer agent), 5.21 g 2,2'-azobis(2-methylbulyloilitrile) and 144 g toluene was added uniformly over 2 hours to a mixture of 225.2 g polyol and 25 g macromer, at 125C with stirring. The mixture was then stirred for a further 30 minutes at 125C. After continuously adding a solution of 0.92 g 2,2'-azobis(2-methylbutyronitrile) in 25.4 g toluene, the ~ ure was stirred for a further hour at 125C, and toluene and other volatile conctitllents were then listill~1 off at 125C, firstly for one hour under water pump vacuum (15 mbar), then for 2 hours under the vacuum from an oil pump (< 2 mbar). After cooling to about 100C, the product was passed through a sieve with a mesh size of 100 ~m.
Run-off test procedure:
About 3 ml polymer polyol were introduced into a 10 ml beaker with a curved rim,the inner walls of which were then completely wetted with polymer polyol by ch~king. After standing for 24 hours at room temperature, the residue rem~ining on the glass walls was ~csessed according to the number of particles of about 5-30 ~um diameter:
good: up to about 10 particles per cm2 average: from about 10 to 30 particles per cm2 poor: more than about 30 particles per cm2.
Examples 1-8:
Polymer polyols with polyol A as the base polyol and macromer A as the macromer were pre~alc;d according to the general preparation specificahion; different chain S h-ansfer agents were used. The reachon was also conducte~1 without a chain hansfer agent, for comparison.
The results are sllmm~ ed in the following Table:
Example Chain hransfer agent viscosity Run-off (mPa. s/25 C) --- 3990 good 2 isopropanol 3760 [1] poor 3 2-butanol 3710 good 4 methyl ethyl ketone 3720 good tehachloromethane 3740 good 6 l-dodecylme~a~l 4990 average 7 enol ether A 3240 good 8 enol ether B 3190 good [1] unfilterable product In this series, enol ethers A and B according to the invenhon gave the lowest vlscosihes.
Examples 9-19:
Polymer polyols with polyol A as the base polyol and macromer B as the macromer were ~epaled according to the general preparation spe~ific~tion; dirre~ t chain S transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
The results are sl-mm~ri~ed in the following Table:
Example Chain transfer agentviscosity Run-off (mPa.s/25C) t2]
isop~opaulol 7450 [1] poor 11 2-butanol 7970 [1] poor 12 methyl ethyl ketone --- [3] ---13 tetrachloromethane 4000 good 14 l-dodecylmerca~tall 29850 poor enol ether A 3550 good 16 enol ether B 3450 good 17 enol ether C --- [3] ---18 enol ether D 4480 average 19 enol ether E 3480 good [1] unfil~erable product [2] the reaction had to be terminated because the batch could no longer be stirred due to its viscosity being too high [3] caked; the reaction had to be termin~ted In this series, enol ethers A, B and E according to the invention gave finely divided, low-viscosity products, whilst enol ethers C and D, which were not according to the Le A 30 960 - 01 ~ 7 ~
invention, and the other chain transfer agents gave dispersions which were unstable or which contained coarse particles and had higher vi~co~iti~.
Examples 2n-27:
s Polymer polyols with polyol A as the base polyol and macromer C as the macromer were pr~ared according to the general preparation specification; different chain transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
The results are summarised in the following Table:
Example Chain transfer agentviscosity Run-off (mPa.s/25C) --~ 4950 tl] poor 21 isopropanol 4330 [1] poor 22 2-butanol 4710 [1] poor 23 methyl ethyl ketone 4630 poor 24 tetrachloromethane 4100 average l-dodecylmercaptan --- [2] ---26 enol ether A 3550 good 27 enol ether B 3300 good [1] unfilterable product [2] the reaction had to be termin~t~d because the batch could no longer be stirred due to its viscosity being too high Enol ethers A and B according to the invention also gave finely divided, low-viscosity products in combination with macromer C, whilst the other chain transfer agents gave dispersions which were unstable or which contained coarse particles and had higher viscosities.
Examples 28-35:
Polymer polyols with polyol A as the base polyol and macromer D as the macromer were ~,epa~ed according to the general pr~al~lion spet~ific~tion; different chain transfer agents were used. The reaction was also cQ~ cted without a chain transfer agent, for comparison.
The results are summ~ri~ed in the following Table:
Example Chain transfer agentviscosity Run-off (mPa.s/25C) 28 --- 19000 [1] poor 29 isopropanol --- t3] ---2-butanol --- [2] ---31 methyl ethyl ketone --- [3] ---32 tetrachlorometh~ne 5840 average 33 l-dodecylme~a~tan 13200 poor 34 enol ether A 3140 good enol ether B 3340 good [1] unfilt~srable product [2] the reaction had to be termin~ted because the batch could no longer be stirred due to its viscosity being too high [3] cakec; the reaction had to be termin~ted.
In combination with macromer D, the advantage of enol ethers A and B according to the invention becomes even clearer. Stable, low-viscosity products were only obtained with the latter.
Examples 3~43:
Polymer polyols with polyol A as the base polyol and macromer E as the macromer were plepaled according to the general preparation specification; different chain transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
The results are summarised in the following Table:
Example Chain transfer agent viscosity Run-off (mPa. s/25 C) 36 7110 [1] poor 37 isopropanol 4800 [1] poor 38 2-butanol 5180 poor 39 methyl ethyl ketone 5100 poor tetrachloromethane 4850 average 41 1 -dodecylmercap~l 5250 average 42 enol ether A 3550 good 43 enol ether B 3260 good [1] unfilterable product Only enol ethers A and B according to the invention gave finely divided, low-viscosity products.
Examples 44-51:
Polymer polyols with polyol A as the base polyol and macromer F as the macromer were prepared according to the general preparation specification; different chain transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
~7 1~ ~3 The results are summarised in the following Table:
Example Chain transfer agent viscosity Run-off (mPa.s/25C) 44 --- [2]
isopropanol --- [2] ---46 2-butanol --- [2] ---47 methyl ethyl ketone --- [2] ---48 tetrachloromethane 6410 poor 49 l-dodecylmercaptan 5870 poor enol ether A 4410 good 51 enol ether B 4020 good [2] the reaction had to be termin~ted because the batch could no longer be stirred due to its viscosity being too high In combination with macromer F, the advantage of enol ethers A and B according to the inventior. becomes particularly clear. Only the latter gave finely divided, low-viscosity dispersions. Dispersions which were either unstable or which containedcoarse particles and had high viscosities were obtained with the chain transfer agents which were not according to the invention.
Examples 5''-59:
Polymer polyols with polyol A as the base polyol and macromer G as the macromer were prepared according to the general preparation specification; different chain transfer agents were used. The reaction was also conducted without a chain transfer agent, for comparison.
The results are summ~riced in the following Table:
~:~ 7 ~
Example Chain transfer agent viscosity Run-off (mPa.s/25 oc) 52 --- 9500 poor 53 isopr~anol 6800 [1] poor 54 2-butanol 6330 poor methyl ethyl ketone 5950 poor 56 tetrachlorome~h~ne 4940 average 57 l-dodecylmercaptan 3800 average 58 enol ether A 3480 good 59 enol ether B 3780 good [1] unfilterable product Only enol ethers A and B according to the invention gave finely divided, low-viscosity products.
Examples 6t)-91:
Use of the polymer polyols according to the invention, from Examples 8, 15, 27, 35, 42, 50 and 59, for the production of flexible foamed materials:
To produce a laboratory foam, all the components - apart from catalyst 3 and thepolyisocyanate - were intensively mixed with each other. Thereafter, catalyst 3 was added, mixed for a short period, and the polyisocyanate was then added with stirring.
The reaction mixture was subsequently poured into an open mould, in which it foamed to form the flexible foam.
The results of the foam tests are summ~n~ed in the following Tables (all amounts in parts by weight).
Catalyst 1: Desmorapid0 DMEA, manufactured by Rhein Chemie, Rheinau Catalyst 2: RC-PUR activator 108, manufactured by Rhein Chelnie, Rheinau Catalyst 3: Desmorapid~ SO, manufactured by Rhein Chemie, Rheinau Stabiliser: Stabiliser OS 22, manufactured by Bayer AG
Isocyanate: toluene diisocyanate (Desmodur'~9 T 80, Bayer AG) Results of foam formulation with a 10 æ filler content (data in % by weight, characteristic number 108, a~arent density about 23 to 24 kg/n~
Ex. 60 Ex. 61 Ex. 62 Ex. 63 Ex. 64 E~. 65 E1~. 66 E~. 67 Polyol A 75 75 75 75 75 75 75 75 Polymer polyol A 25 Example 8 25 E~cample 15 25 Example 27 25 Example 35 25 Example 42 25 Example 50 25 Example 59 25 Water 4 5 4 5 4 5 4 5 4 5 4-Stabiliser Catalyst 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Catalyst 3 0.13 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Foaming capacity very good very good very good very good very good very good very good very good Open cellularity very good very good very good very good very good very good very good very good Apparent density according to DIN 53 420 (kg/m3) 23 24 24 23 24 24 24 24 Tensile strength ~ rd;l,g to DIN 53 571 (kPa) 121 126 126 145 137 123 146 128 Breaking elongation acco,d;.,g to DIN 53 571 (%) 131 103 117 128 123 97 125 101 40 % Strain hardness according to DIN 53 577 (kPa) 4.4 5.5 4.9 5.1 5.3 5.6 5.4 5.7 Grip/elasti.;il~ very good very good very good very good very good very good very good very good Results of foam formulation with a 20 % filler content (data in % by weight, chd,~ctelistic number 108, apparent density about 23 to 24 kg/m3 Ex. 68 Ex. 69 E~c. 70 Ex. 71 E~c. 72 E~c. 73 Ex. 74 E~. 75 Polyol A 50 50 50 50 50 50 50 50 Polymer polyol A 50 Example 8 50 Example 15 50 Example 27 50 Example 35 50 Example 42 50 Example 50 50 Example 59 50 Water 4 5 4 5 4 5 4 5 4 5 Stabiliser Catalyst 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Catalyst 3 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 Foaming capacity very good very good very good very good very good very good very good very good Open cellularity very good very good very good very good very good very good very good very good Apparent density according to DIN 53 420 (kg/m3) 23 23 23 23 23 24 23 23 Tensile strength dccoldillg to DIN 53 571 (kPa) 147 121 148 144 148 144 137 141 Breaking elongationaccording to DIN 53 571 (%) 126 95 97 86 100 102 103 108 40 % Strain hardness accor.ling to DIN 53 577 (kPa) 5.7 6.1 6.1 6.8 6 6.1 5.9 5.6 Grip/el~t;~,;t~ very good very good very good very good very good very good very good very good Results of foam formulation with a 10 % filler content (data in % by weight, chal~t.,.i~lic number 108, apparent density about 37 to 39 kg/m3 Ex. 76 Ex. 77 E~c. 78 E~c. 79 Ex. 80 Ex. 81 Ex. 82 E~t. 83 Polyol A 75 75 75 75 75 75 75 75 Polymer polyol A 25 Example 8 25 Example 15 25 Example 27 25 Example 35 25 Example 42 25 Example 50 25 Example 59 25 Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stabiliser 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Catalyst 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Catalyst 3 0.13 0.12 0.12 0.12 0.12 0.12 0.12 0.12 Foaming capacity very good very good very good very good very good very good very good very good Open cellularity very good very good very good very good very good very good very good very good Apparent density according to DIN 53 420 (kg/m3) 37 38 38 38 38 39 38 38 Tensile strength r-~c .lillg to DIN 53 571 (kPa) 156 142 104 160 149 147 157 146 Breaking elongation accol.l;ng to DIN 53 57l (%) 155 142 114 156 141 138 145 148 j, 40 9to Strain hardness according to DIN 53 577 (kPa) 5.6 5.2 5 5.3 5.4 5.3 5.5 5.4 Grip/cla~ very good very good very good very good very good vely good very good very good Results of foam formulation with a 20 % filler content (data in % by weight, cLa.~ leristic number 108, apparent density about 37 to 39 kg/m3 F.x. 84 Ex. 85 Ex. 86 Ex. 87 Ex. 88 Ex. 89 E~c. 90 E~. 91 Polyol A 50 50 50 50 50 50 50 50 Polymer polyol A 50 Example 8 50 Example 15 50 Example 27 50 Example 35 50 Example 42 50 Example 50 5 Example 59 Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stabiliser 0.7 0.7 0.7 0.7 07 0 7 07 0 7 Catalyst 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Catalyst 2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Catalyst 3 0.13 0.12 0.12 0.12 0.12 0.12 0.12 0.12 Foaming capacity very good very good very good very good very good very good very good very good Open cellularity very good very good very good very good very good very good very good very good Apparent density acco.dh~g to DIN 53 420 (kg/m3) 36 38 38 37 38 39 37 39 Tensile strength acco.. li.. g to DIN 53 571 (kPa) 182 159 187 195 181 162 166 173 Breaking el~-nga~ion according to DIN 53 571 (%) 148 109 131 146 131 108 121 110 40 % Strain hardness according to DIN 53 577 (kPa) 6.4 6.9 6.6 6.6 6.8 6.8 6.6 7 Grip/elasticity very good very good very good very good very good very good very good very good Foaming examples 60 - 91 show that the finely divided, low-viscosity polymer polyol dispersions according to the invention result in foams, the propel~ies of which are col.-pa,~ble with current commercial products of higher viscosity. On account of their lower viscosity at a given filler content, foam formulations based on the products according to the invention can be processed more easily. Moreover, higher solidscontents, which result in foams of correspondingly greater hardness, can be obtained with them, taking an identical maximum processing viscosity into consideration.
Comparative Examples 1 to 6:
For comparison purposes, polymer polyols were prepared in the presence of enol ethers without the addition of macromer.
A mixture conci~ting of 375.3 g polyol, 250 g styrene, 166.8 g acrylonitrile, 8.34 g enol ether A, 5.2 g 2,2'-azobis(2-methyl-butyronitrile) and 144 g toluene was added uniformly over 2 hours to 250.2 g of polyol, with stirring, in a nitrogen atmosphere at 125C. The mixture was stirred for a further 30 minutes at 125C. After the continuous addition of a solution of 0.9 g 2,2'-azobis(2-methyl-butyronitrile) in 25.4 g toluene, stirring was continued for a further hour at 125C, and then toluene and other volatile concti~lents were distilled off at 125C, firstly for one hour under the vacuum from a water pump (15 mbar) and then for 2 hours undel the vacuum from an oil pump (< 2 mbar). After cooling to about 100C, the product was passed through a sieve of mesh aperture 100 ~m.
The results of the comparative tests are summarised in the following Table.
Comparison Polyol Enol Viscosity Progress Example ether (MPas/25C) Polyol A - caked [1]
2 Polyol A Vulkazon caked [1]
AFD
3 Polyol D
4 Polyol D Vulka~on highly [2]
AFD viscous Polyol E - 21,780 poor 6 Polyol E Vulkazon 7180 poor AFD
[1] dispersion unstable; reaction had to be stopped [2] the reaction mixture was so viscous that the reaction had to be stopped The comparative tests show that only undesirably highly viscous or caked polymer polyols are obtained without the addition of macromers.
Claims (11)
1. A process for producing stable, low-viscosity graft copolymer dispersions which are free from agglomerates by the radical polymerisation of ethylenically unsaturated monomers in a base polyol, characterised in that the polymerisation is effected in the presence of a polyol containing ethylenically unsaturated terminal groups and an enol ether of the following general formula A=CH-O-R
where A is a divalent radical of formula R represents a C1-18 alkyl, C5-10 cycloalkyl or optionally a benzyl radical with a substituted nucleus, and R' represents hydrogen or a C1-8 alkyl radical, optionally in the presence of an organic solvent.
where A is a divalent radical of formula R represents a C1-18 alkyl, C5-10 cycloalkyl or optionally a benzyl radical with a substituted nucleus, and R' represents hydrogen or a C1-8 alkyl radical, optionally in the presence of an organic solvent.
2. A process according to claim 1, characterised in that amount of ethylenically unsaturated monomers is 25-65 % by weight with respect to the total amount of monomers and polyol.
3. A process according to claims 1 and 2, characterised in that styrene and acrylonitrile in a weight ratio of 20:80 to 100:0 are used as the ethylenically unsaturated monomers.
4. A process according to claims 1 and 2, characterised in that styrene and acrylonitrile in a weight ratio of 50:50 to 80:20 are used as the ethylenically unsaturated monomers.
5. A process according to claims 1 to 4, characterised in that a polyalkylene oxide containing two to six hydroxyl groups and with an OH number of 20 to 100, preferably 30 to 70, is used as the base polyol.
6. A process according to claims 1 to 5, characterised in that a base polyol ofmolecular weight 1800 to 4500, preferably of molecular weight 2000 to 4000, is used.
7. A process according to claims 1 to 6, characterised in that a polyol is used which has a functionality of two to six, which contains ethylenically unsaturated terminal groups, and which has a molecular weight of 3000 to 15,000, preferably a molecular weight of 4500 to 12,000.
8. A process according to claims 1 to 7, characterised in that the polyol containing ethylenically unsaturated terminal groups is used in an amount of 2-20 % by weight, preferably 3 to 10 % by weight, with respect to the total amount of base polyol.
9. A process according to claims 1 to 8, characterised in that (cyclohex-3-enylidenemethoxymethyl)-benzene is used as the enol ether, in an amount of 0.1 to 5 % by weight with respect to the amount of monomer used.
10. Stable low-viscosity graft copolymer dispersions which are free from agglomerates, obtainable by the process according to claims 1 to 9.
11. Use of the graft copolymers obtainable according to claims 1 to 9 as polyol components in the production of polyurethane foamed materials.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19508578 | 1995-03-10 | ||
| DE19508578.7 | 1995-03-10 | ||
| DE19533164.8 | 1995-09-08 | ||
| DE19533164A DE19533164A1 (en) | 1995-03-10 | 1995-09-08 | Low-viscosity polymer polyols, a process for their preparation and their use in the production of polyurethane foams |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2171163A1 true CA2171163A1 (en) | 1996-09-11 |
Family
ID=26013231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002171163A Abandoned CA2171163A1 (en) | 1995-03-10 | 1996-03-06 | Low-viscosity polymer polyols, a process for producing them, and their use for the production of polyurethane foamed materials |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0731118B1 (en) |
| JP (1) | JPH08259641A (en) |
| CN (1) | CN1066743C (en) |
| CA (1) | CA2171163A1 (en) |
| ES (1) | ES2164176T3 (en) |
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| DE19545123C1 (en) * | 1995-12-04 | 1997-02-13 | Basf Lacke & Farben | Radiation-curable coating composition and its use for coating |
| US6624209B2 (en) | 1999-07-30 | 2003-09-23 | Sanyo Chemical Industries, Ltd. | Polymer polyol composition, process for producing the same, and process for producing polyurethane resin |
| US6756414B2 (en) | 1999-07-30 | 2004-06-29 | Sanyo Chemical Industries, Ltd. | Polymer polyol composition, process for producing the same, and process for producing polyurethane resin |
| US7160975B2 (en) * | 2004-08-02 | 2007-01-09 | Bayer Materialscience Llc | Methacrylates as stabilizers for polymer polyols |
| CN102471445B (en) | 2009-07-20 | 2014-05-28 | 巴斯夫欧洲公司 | Method for producing viscoelastic polyurethane flexible foam materials |
| JP5458737B2 (en) * | 2009-08-18 | 2014-04-02 | ソニー株式会社 | Resin composition, thermal transfer sheet, and method for producing thermal transfer sheet |
| CA3183122A1 (en) | 2020-05-14 | 2021-11-18 | Basf Se | Electrically dissipative polyurethane foams and use thereof in trench breakers or pipeline pillows |
| TW202214734A (en) | 2020-06-22 | 2022-04-16 | 德商巴斯夫歐洲公司 | Viscoelastic elastomeric polyurethane foams, process for preparing them and use thereof |
| EP4185628A1 (en) | 2020-07-24 | 2023-05-31 | Basf Se | Multilayered structure and a process for preparing the same |
| WO2023036801A1 (en) | 2021-09-07 | 2023-03-16 | Basf Se | Ionic monomer- based polyurethane foams and use thereof in trench breakers or pipeline pillows or thermally insulative material |
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| DE2837026A1 (en) * | 1978-08-24 | 1980-03-06 | Bayer Ag | METHOD FOR PRODUCING MODIFIED POLYAETHERPOLYOLS |
| US4661531A (en) * | 1984-03-21 | 1987-04-28 | Basf Corporation | Process for preparing graft polymer dispersions and polyurethanes prepared therefrom |
| US4522976A (en) * | 1984-05-17 | 1985-06-11 | Basf Wyandotte Corporation | Graft polymer dispersion in a mixture of low molecular weight polyols and polyether polyols and polyurethane foams prepared therefrom |
| US4568705A (en) * | 1984-05-17 | 1986-02-04 | Basf Wyandotte Corporation | Graft polymer dispersion in a mixture of low molecular weight polyols and polyether polyols and polyurethane foams prepared therefrom |
-
1996
- 1996-02-27 ES ES96102878T patent/ES2164176T3/en not_active Expired - Lifetime
- 1996-02-27 EP EP96102878A patent/EP0731118B1/en not_active Expired - Lifetime
- 1996-03-06 CA CA002171163A patent/CA2171163A1/en not_active Abandoned
- 1996-03-06 JP JP8075380A patent/JPH08259641A/en active Pending
- 1996-03-08 CN CN96103070A patent/CN1066743C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| ES2164176T3 (en) | 2002-02-16 |
| CN1066743C (en) | 2001-06-06 |
| EP0731118A2 (en) | 1996-09-11 |
| EP0731118A3 (en) | 1998-04-29 |
| EP0731118B1 (en) | 2001-10-17 |
| JPH08259641A (en) | 1996-10-08 |
| CN1135492A (en) | 1996-11-13 |
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