DE2728284A1 - POLYMER / POLYOL PREPARATIONS - Google Patents

Description

The present invention relates to new polymer / polyol preparations, which are reactive with polyisocyanates in the manufacture of polyurethane products. The present invention relates further to new methods of making these preparations and to methods of making polyurethane products from these.

Polymer / polyol dispersions have been and are currently being used in the Used in the manufacture of polyurethane products. These dispersions result in polyurethane products of many different types desirable properties.

There are numerous publications on the production of Polyiner / polyol disperse ions, such as US PSS 3 304 273, 3 383 351 and Re 28 715 (reissue of 3 383 351), the GB PS 1,022,434, Canadian Patents 735,010 and 785,835, U.S. Patent 3,823,201, U.S. Patent Application Ser 7.1.1974 and US PSS 3,953,393 and 3,655,553.

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The patent specifications mentioned from GB PS 1 022 434 onwards describe the production of polymer /

Polyol dispersions by polymerizing one or more Ethylenically unsaturated monomers in situ in a polyol with the formation of dispersions of small poly-■ particles dispersed in the polyol. Then the dispersions are mixed with polyisocyanate and other polyurethane-forming reactants and implemented to form the polyurethane product and serve as a convenient, effective and economical means of improvement the obtained polyurethane properties. This method and the resulting polymer / polyol dispersions have been and are widely accepted by the polyurethane industry continues to be used extensively by the industry

Although the known polymer / polyol dispersions intensively from The entire polyurethane industry has been used, has the development of more complicated plants, machines and systems of higher speed and larger volume for handling, mixing and converting the polyurethane-forming components Need created to improve polymer / polyol dispersions · There has been a need for more stable dispersions

developed so that you can do this without noticeable settling up to

("seediness") Use can store. In the past, the settling properties »/ the viscosity or filterability of polymer / polyols in the Little attention is paid to actual large-scale use. However, the technique of polyurethane production is like that far advanced that these considerations are of the utmost importance. Filterability, settling properties and viscosity are now due to the more complicated machine systems

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Manufacture of large volumes of importance. Furthermore, the well-known dispersions with the relatively low molecular weight polyols, like dipropylene glycols, not in an extremely stable state produced what the lower molecular weight materials less desirable than higher molecular weight materials for the Polyol component made of the polymer / polyol dispersions. the Lower molecular weight polyols are of value in cases where low viscosity is important, as well as for foams, coatings and certain types of sealants

The present invention provides extremely stable and filterable Polymer / polyol preparations that have little tendency to settle ("seedi-

or
ness ") have / are practically free of this. Furthermore, a relatively higher polymer content in the dispersion at low viscosities is possible without impairing the stability. These and other advantages are achieved by using a small amount of higher molecular weight polyol in the lower molecular weight polyol .

The use of polyol blends to make polymer / polyols has been described in many of the publications cited above. The use of low molecular weight polyols in polymer / poly dispersions was mentioned in CB PS 1 022 434 /. However, in no publication is there a description or reference to the advantages established according to the invention through the addition of a small amount of a higher molecular weight polyol to a lower molecular weight polyol according to the present description.
/ ♦ as well as almost all of the patent specifications mentioned above

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U.S. Patent 3,655,553 describes that the polyol is preferably a triol, but can contain up to 40% of a diol or tetrol of the same molecular weight range. The molecular weights of the polyols are not more than 5500, are preferably not more than 5000 and are expediently in the range from 1500-5000, preferably 3000-5000.

U.S. Patent 3,823,201 describes the use of a polyol blend from two polyols with the same molecular weights. US patent application 431 080 describes the preparation of polymer / polyol dispersions from polyol blends and vinyl or vinylidene halide monomers and claims' Improvements in Stability · According to the application, it was found to be stable, of Graft copolymer dispersions derived from vinyl monomers at temperatures below 100 ° C. and in the absence of auxiliary chain transfer agents Can produce if the monomer vinyl chloride, vinyl bromide, vinylidene chloride or vinylidene bromide is. The polymer / polyols made from halogenated monomers can interfere with the manufacture of polyurethane products and are in many cases unacceptable for such use, because they form acidic decomposition products that interfere with the catalyst.

USPS 3,953,393 describes the preparation of polymer / polyol dispersions by polymerizing vinyl monomers in the presence of alkyl mercaptans as chain transfer agents in specially formulated polyols containing unsaturated bonds that contain specific, apparently critical amounts of unsaturated Have ties. Such polymer / polyol dispersions are for

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Only very limited use in the polyurethane field due to the bad odor of the polyurethane products made from them suitable This bad smell comes from the alkyl mercaptan chain transfer agent, which according to the patent specification is necessary for the production of the polymer / polyol dispersions and such products for the consumer, especially in the case of mattresses or armrests, Impact pad, etc., unacceptable. The use of alkyl mercaptans required by this patent specification brings also considerable processing problems due to the extremely unpleasant and strong odor of the mercaptans and their harmful Effect on those employed in the manufacture or use of the dispersions.

None of the above publications and no prior art describes, teaches or implies stable polymer / polyols the advantageous properties of the preparations according to the invention, which are obtained from ethylenically unsaturated monomers through use of mixtures of a large amount of a low molecular weight polyol and a small amount of a higher molecular weight polyol getting produced.

The present invention provides polymer / polyol preparations that are extremely stable and extremely filterable; furthermore, they can be highly flowable and practically free of waste material and lumps.

("seeds")
chen / be. The polymer particles of the preparations according to the invention are of small size and, in a preferred embodiment, less than 30 microns in diameter. According to the invention, the polymer / polyol preparations can be produced with exceptionally low viscosities. You can also use them with a relatively high

Produce polymer content. The polymer / polyol according to the invention

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Preparations are easy to use in polyurethane products with exceptional Properties convertible, which in certain cases have a high

(Load capacity)
Load-bearing capacity and high resistance to discoloration and

grasp.

The above-mentioned shortcomings of the known prior art can according to the invention by adding a small amount of a higher molecular weight Polyol to be overcome to the base polyol with lower molecular weight, which is used for the production of the polymer / polyol preparations Intended to use · No halogenated monomers need to be used in the subsequent polyurethane production can be harmful. Furthermore, you do not need such foul-smelling and unpleasant materials, such as alkyl meroaptans, to be used «

The present invention generally achieves the above advantages by creating stable liquid polymer / polyol preparations that convertible into polyurethane products by reaction with polyisocyanates are, with the polyroer / polyol preparation usually at the conversion temperature of the preparation into the polyurethane product is liquid and the polymer / polyol preparation is made in situ in the absence of any alkyl mercaptan in the polyol or more polymerizable »!, ethylenically unsaturated monomers s that are practically free of chemically bound halogen, The polymer / polyol preparations according to the invention are at 25 ° C. preferably liquid. The present invention creates stable dispersions of small particles of the polymer in the polyol by in .situ polymerization of the monomer or a Monomer mixture in a polyol mixture of about 55-95 percent by weight of a polyol with a numerical average MoIe-

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kul ar weight not over about 4000 and about 45-5 wt .- $ one Number average molecular weight polyols not under etωa 5000. Another advantage of the invention lies in the fact that there is a wider range of free radical catalyst used in the polymerization without critically narrow limitations and without impairing stability or filterability can be. So you can, for example, if necessary or necessary Azo and peroxide catalysts are used, and you can Select safer and more easily disposable catalysts.

The present invention further relates to the method for the manufacture of the above-mentioned preparations as well as the process for the manufacture of polyurethane products using the same. The polymer / polyol preparations according to the invention are by reaction with polyisocyanates in polyurethane elastomers and High modulus foams convertible

The polymer / polyol preparations according to the invention are liquid, stable dispersions of polymer in a polyol mixture of approx 55-95 wt .- ^, preferably about 70-90 wt .- ^ of one or more Polyols with a number average molecular weight not exceeding AOOO, hereinafter also referred to as low molecular weight or NM polyol, and about 5-45 wt. Ji, preferably about 10-30 Gew .- ^ one or more polyols with a numerical average molecular weight not below about 5000, which is also referred to below as higher molecular weight or HM polyol, where the percentages by weight are based on the total weight of NM and HM polyols in the preparation. There is practically no lower one Limit for the molecular weight of the NM polyol nor an upper limit for the molecular weight of the HM polyol, as long as the

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Polyol liquid and and the mixture and the final polymer / polyol have the desired viscosities · The molecular weight the NM polyol can be as low as that of dipropylene glycol and is preferably between about 400,000,000, especially about 1000-4000. The molecular weight of the HM polyol is preferably about 5000-20,000, in particular about 6000-15,000. The respective molecular weights are the critical parameters in comparison to the respective equivalent weights; i.B. became no Difference between a diol or a triol as an HM or NM polyol found in achieving the advantages of the invention when the molecular weights are really the same. In the present case the number average molecular weights of the PdLyols are used; these are the theoretical (or obvious), values calculated from the theoretical functionality and the hydroxyl number. The real numerical average molecular weight can be a little lower, depending on how much the real functionality is below the initial or theoretical Functionality lies. To achieve stable dispersions, the NM and the HM polyol should be compatible with one another.

The polymer content in the polymer / polyol preparations according to the invention can be between about 4-40 wt .-%, preferably about 15-35 wt .- % , based on the total weight of the polymer / polyol preparation.

Any polyol used to date for the production of polymer / polyols can be used according to the invention for the HM and NM polyols, provided that it meets the above requirements with regard to the Holistic average molecular weight and mutual Compatibility.

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Suitable polyols for the production of the polymer according to the invention / Polyol preparations and the polyhydroxyalkanes, the polyoxyalkylene polyols usis. The suitable polyols can be selected from one or more of the following classes of preparations alone or in a mixture selected in the usual way ω earth:

(a) alkylene oxide adducts of polyhydroxyalkanes,

(b) alkylene oxide adducts of non-reducing sugars and Sugar derivatives,

(c) alkylene oxide adducts of phosphoric and polyphosphoric acid;

(d) alkylene oxide adducts of polyphenols,

(e) the polyols of natural oils such as castor oil, uside.

Suitable alkylene oxide adducts of polyhydroxyalkanes include e.g. the alkylene oxide adducts of ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1, A-, 1,5- and 1,6-dihydroxyhexane, 1,2-, 1,3-, 1,4-, 1,6- and 1,8-dihydroxyoctane, 1,10-oxydecane, glycerol, 1,2,4-trihydroxybutane, 1,2,6-trihydroxyhexane, 1,1,1-trimethylolethane, 1,1,1-triroethylolpropane, pentaerythritol, caprolactone, polycaprolactan, Xylitol, arabitol, sorbitol, mannitol, etc. «. A preferred class of alkylene oxide adducts of the polyhydroxyalkanes are the ethylene oxide, Propylene oxide, butylene oxide adducts of trihydroxyalkanes or mixtures of the same

Another class of suitable polyols are the alkylene oxide adducts the non-reducing sugars in which the alkylene oxides have 2-4 carbon atoms. Suitable non-reducing sugars and sugar derivatives are sucrose, alkyl glycosides such as methyl, ethyl glucoeide etc., glycol glycosides, such as ethylene glycol glucoside, propylene glycol glucoside, Glycerol lucoid, 1,2,6-hexanetriol glucoside, etc.

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as well as the alkylene oxide adducts of alkylglycene in accordance with US PS 3,073,788.

Also suitable as polyols are the polyphenols, preferably the alkylene oxide adducts thereof, in which the alkylene oxides Have 2-4 carbon atoms. Suitable polyphenols are e.g. bisphenol A, bisphenol F, condensation products of phenol and formaldehyde, the novolak resins, condensation products of various phenolic Compounds and acrolein, the simplest member of this class being the 1,1,3-tris (hydroxyphenyl) propane, condensation products various phenolic compounds and glyoxal, glutaraldehyde and other dialdehydes, being the simplest members of this class are the 1,1,2,2-tetrakis (hydroxyphenol) ethanes, etc.

Also suitable as polyols are the alkylene oxide adducts of phosphoric and polyphosphoric acids. Preferred alkylene oxides are Ethylene oxide, 1,2-epoxypropane, the epoxy butane, 3-chloro-1,2-epoxypropane etc. In this context, phosphoric acid, phosphorous acid, the polyphosphoric acids, such as tripolyphosphoric acid, the polymetaphosphoric acids, etc.

The polyols used can have hydroxyl numbers that are above vary over a wide range. Usually the hydroxyl number of the polyols used according to the invention are between about 20 and below to about 850 and higher. The hydroxyl number becomes defined as the number of mg of potassium hydroxide required for complete hydrolysis of the completely acetylated polyols produced from 1 g Derivatives is necessary. It can also be defined by the following equation:

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OH - 56.1 χ '1000 χ f m.ui.

It is

OH s hydroxyl number of the polyol

f & functionality, i.e. average number of hydroxyl groups per molecule of polyol

n · »· = molecular weight of the polyol.

The exact polyol used will depend on the end use of the one being made Polyurethane product. The molecular weight or the hydroxyl number are selected accordingly to be flexible or To obtain semi-flexible foams or elastomers when the polymer / polyol made from the polyol is converted into a polyurethane will. The polyols preferably have a hydroxyl number of about 50-150 for semi-flexible foams and about 30-70 for flexible foams «These values are not a limitation, but are purely an illustration of the large number of possible Combinations of the above polyol corporates.

The most preferred polyols of the present invention include the poly (oxypropylene) glycols, triols, and higher functional polypols; they also include poly (oxypropylene-oxyethylene) polyols. However, it is expedient that the oxyethylene content is less than 80 % of the total mass, preferably less than 60 % . The optionally used ethylene oxide can be incorporated in any way along the polymer chain. That is, the ethylene oxide can either be incorporated in internal blocks, as terminal blocks, or randomly distributed along the polymer chain. It is known that the most preferred polyols here contain different small amounts of unsaturated bonds. According to US PSS 3 304 273, 3 3B3 351 and GB PS 1 022 434,

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does the unsaturation itself in no way affect the formation of the polymer / polyols according to the invention, with the exception of where the degree or type of unsaturation is so high or effective, that this leads to a crosslinked polymer.

The polymerizable, ethylenic which can be used according to the invention Unsaturated monomers include materials that are free of bound halogen. Such monomers include the polymerizable, ethylenically unsaturated carbon monomers and polymerizable, ethylenically unsaturated organic monomers, their molecules of carbon, hydrogen and at least one Element of 0, S or N are composed · The in the invention Process suitable monomers are the polymerizable monomers, which by the presence of at least one polymerizable, Ethylenically unsaturated group of the type C = C

are. The monomers can be used individually or in combination to form responsive

used by / homopolymer polyol or / mixed polymer / polyol preparations will. '

These monomers are known and include the carbon monomers, such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene, o (-methylstyrene, methylstyrene, 2,4-dimethyletyrene, Ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, Cyclohexyl styrene, benzyl styrene, etc .; substituted styrenes, such as cyanogen styrene, nitrostyrene, Ν, Ν-dimethylaminostyrene, acetoxystyrene, Methyl 4-vinyl benzoate, phenoxystyrene, p-vinyl diphenyl sulfide, p-vinylphenylphenyl oxide, etc .; the acrylic and substituted Acrylic monomers, such as acrylic acid, methacrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methyl methacrylate, Cyclohexymethacrylate, benzyl methacrylate, isopropyl methacrylate,

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Octyl methacrylate, methacrylonitrile, ethyl ot-ethoxy acrylate, methyl «(- acetaminoacrylate, butyl acrylate, 2-ethylhaxylacrylate, phenyl acrylate, Phenyl methacrylate, Ν, Ν-dimethylacrylamide, N, N-dibenzylacrylamide, N-butyl acrylamide, methylacrylylformamide, etc .; the vinyl esters, Vinyl ethers, vinyl ketones, etc., such as vinyl acetate, vinyl alcohol, vinyl butyrate, isopropenyl acetate, vinyl formate, vinyl acrylate, Vinyl methacrylate, vinyl methoxyacetate, vinyl benzoate, vinyl toluene, Vinyl naphthalene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, Vinyl butyl ether, uinyl-2-ethylhexyl ether, vinyl phenyl ether, Vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, Vinyl 2-ethylraercaptoethyl ether, vinyl methyl ketone, vinyl ethyl ketone, Vinyl phenyl ketone, vinyl ethyl sulfide, vinyl ethyl sulfone, N-ethyl-N-vinylacBtamide, N-uinylpyrrolidone, vinylimidazole, divinyl sulfide, Divinyl sulfoxide, divinyl sulfone, sodium vinyl sulfonate, Methyl vinyl sulfonate, N-vinyl pyrrole, etc .; Dime thy lfutna rat, dimethyl maleate, maleic acid, crotonic acid, fumaric acid, itaconic acid, monoethyl itaconate, tert-butylaminoethyl methacrylate, dirnethylaminoethyl methacrylate, Glycidyl acrylate, allyl alcohol, glycol monoesters of itaconic acid, vinyl pyridine, etc. Any of the known poly nerisable monomers are used, the above list being used for illustration and with respect to the invention suitable monomers is not a limitation. Any known chain transfer agent other than the alkyl mercaptans can be used to be present·

The for the production of the polymer of the polymer according to the invention / The preferred monomers used in polyol preparations is acrylonitrile alone as a homopolymer or in combination with styrene as

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Mixed polymer. The relative weight ratios of acrylonitrile to styrene are, for example, between about 20:80 to 100: 0, preferably between about 25:75 to 100: 0; become low molecular weight Polyols, e.g. used with a molecular weight below about 200, then the weight ratio should in particular be between about 60:40 to about 85:15. Copolymers of acrylonitrile, methyl methacrylate and styrene can also be used.

The for the production of the polymer / polyol preparations according to the invention Suitable catalysts are free radical vinyl polymerization catalysts, such as peroxides, persulfates, perborates, percarbonates and azo compounds or all others in the above Catalysts indicated in the literature, such as 2,2-azo-bisisobutyronitrile, Dibenzoyl peroxide, lauroyl peroxide, di-tert.-butyl peroxide, Diisopropyl peroxide carbonate, tert-butyl peroxy-2-ethylhexahoate, tert-butyl perpivalate, 2,5-dimethylhexane-2,5-di-per-2-ethylhexoate, tert-butyl perneodecanoate, tert-butyl perbenzoate, tert-butyl percrotonate, tert-butyl perisobutyrate, di-tert-butyl perphthalate etc. Azobis- (isobutyronitrile) is the preferred catalyst as it does not give the product any unpleasant odor and does not require any special handling in the system due to possible dangers.

The catalyst concentration is not critical and can be varied within wide limits; it can, for example, from about 0.1-5.0 Wt .-%, based on the total feed to the reactor, vary. Up to a certain point, increased catalyst concentrations lead to increased monomer conversion, a further increase however, no longer increases the conversion significantly. Against it

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an increased catalyst concentration improves the product stability Usually the catalyst concentration chosen will be an optimal one taking into account all factors including cost Value.

The polymerization can also be carried out with an inert organic solvent that the polymer does not dissolve. Toluene and benzene are suitable, including those for the polymerisation of vinyl monoromers known suitable solvents. The only requirement regarding the choice of solvent and polyol is that that they do not interfere with the polymerization of the monomer. If an inert organic solvent is used, it will usually be from the reaction mixture in the usual way before the use of the polymer / polyols for the production of polyurethane foams removed.

The temperature range is not critical and can range from about 80 ⁰ C. or less to about 15O ⁰ C. or more, preferably 105-135 ⁰ C, vary. The catalyst and temperature should be selected so that the catalyst has a reasonable rate of decomposition relative to residence time in the case of a continuous flow reactor or feed time for a semi-batch reactor.

That for the production of the polymer / polyol preparations according to the invention preferred method is carried out with polymerization of the monomers in the polyol, a low ratio of monomer to polyol being maintained during the polymerization in the entire reaction mixture will. This, in the preferred case, creates a polymer / polyol preparation in which virtually all of the polymer particles are one

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Are less than 30 microns in diameter, and usually less than 1 micron, Such low l / ratios are achieved by using Process conditions which result in rapid conversion of the monomer to polymer. In practice a low monomer to polyol ratio will be used sustained, namely with the half-paragraph and continuous operation by controlling temperature and mixing conditions, and in the case of semi-batch operation also by slowly adding the monomers to the polyol · The process can be done in various ways, e.g. by means of half paragraphs Reaction, in a continuous backmixed stirred tank reactor usui. take place. For the latter, a second step to increase the monomer conversion step by step can be used. It will such mixing conditions are applied as can be achieved by using a backmix reactor (e.g. a stirred flask or autoclave) achieved. These reactors keep the reaction mixture relatively homogeneous and thus prevent localized high ratios of monomers) to polyol, which occur in certain tubular reactors (e.g. in the first stages of "Marco" reactors, if such reactors be operated in the usual manner with the addition of all of the monomer in the first stage).

When using a semi-batch process, the loading times can (as well as the polyol content in the reactor at the beginning compared to the polyol feed with the monomer) can be varied in order to Bring about changes in the product viscosity. Usually longer loading times result in higher product viscosities and also allow slightly wider ranges of acrylonitrile to styrene to be used for a given polyol and polymer content.

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The raw polymer / polyql preparations usually contain minor amounts Amounts of unreacted monomers. These residual monomers can be converted into further polymer by working in two stages be in which the product from the first stage

(of the backmixing reactor) is passed into a second stage, which is a Marco reactor operated in the usual way or a tank reactor can be without stirring.

The preferred temperature for the preparation of the polymer / polyol preparations according to the invention is any temperature at which the half-life of the catalyst is not more than about 25 % of the residence time in the reactor. For example, the half-life of the catalyst at a given reaction temperature cannot be longer than 6 minutes (preferably not longer than 1.5-2 minutes). The half-lives of the catalysts become shorter with increased temperature. For example, azobisisobutyronitrile has a half-life of 6 minutes at 100 ^° C. The maximum temperature used is not particularly critical, but should be lower than the temperature at which there is noticeable decomposition of the reactants or products.

In the one sent for the production of the polymer / polyols according to the invention In this process, the monomers in the polyol are polymerized. Usually the monomers are soluble in the polyol. It was found, that a first dissolution of the monomers in a small proportion of polyol and adding the solution so formed to the remaining polyol the reaction temperature the mixing of monomers and polyol and can reduce or eliminate fouling of the reactor. If the monomers are not soluble in the polyols known methods (such as dissolving the insoluble

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Conomors in another solvent) can be used to disperse the monomers in the polyol prior to polymerization. The monomer conversion in polymers by this process is remarkably high, eg conversions of at least 72-95% of the monomers are usually achieved.

In the copolymerization of acrylonitrile and styrene, the ratio of acrylonitrile to styrene in the polymer is always something lower than the ratio of acrylonitrile to styrene monomer in the feed because the styrene often reacts a little faster than the acrylonitrile. For example, if acrylonitrile and styrene monomers were introduced at a weight ratio of 80:20, then the resulting polymer has an acrylonitrile / styrene weight ratio of about 79:21 or 78:22.

The inventive method yielded extremely stable polymer / Polyol preparations, which are further characterized by a relatively high polymer content, small polymer particle size, freedom from waste and lumps and their convertibility into extremely valuable polyurethane elastomers and foams are labeled. With a given polyol, the present invention particularly allows an increase in the ratio of styrene to acrylonitrile or the polymer content, while products with improved Stability can be obtained. Furthermore, more stable polymer / polyols with lower molecular weight polyols are obtained than with the known ones Procedure was possible. The polymer according to the invention / Polyol preparations are stable dispersions, so that practically all polymer particles are suspended for several months on standing stay and show no noticeable settling.

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The polymer / polyols according to the invention comprise dispersions in which the polymer particles (as individual particles or agglomerates thereof) are of relatively small size and, in the preferred embodiment, practically all below 30 microns. In the preferred embodiment, virtually all of the product, ie about 99 % or more by the filter used in the filtering test of the examples. This allows the polymer / polyol products to be successfully processed in all types of relatively complex machine systems currently used for the large-scale manufacture of polyurethane products, including those which employ impingement-type mixing which requires the use of filters that cannot tolerate appreciable amounts of relatively large particles. Less stringent demands are satisfied when around 50 % of the product goes through the filter. For some purposes, products are also suitable in which only about 20 % pass the filter. The polymer / polyols according to the invention therefore comprise products in which at least 20 %, preferably at least 50 % and in particular practically the entire mass passes through the filter.

The polymer / polyol dispersions of the invention have one higher than normal polymer content in glycols or other, very low molecular weight polyols and still have technical valuable Features such as low waste content, low content of filterable solids and no tendency to settle. The polymer / polyols are usually stable, insoluble dispersions Polymers (e.g. acrylonitrile polymers or acrylic

Polymers

nitrile / styrene polymeric polymers or / all other monomer systems)

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in a base polyol. It is known that the molecular weight of the base polyol has a significant effect on the dispersion stability of the polymer / polyol. Usually, the higher the molecular weight of the base polyol, the better the dispersion stability. This is why the production of stable polymer / polyols in low molecular weight polyols has previously been so difficult. According to the invention, the addition of a fine small amount, ie 5-45 %, of a high molecular weight polyol (Κοΐ.-geuu 5000 or more) to a low molecular weight polyol leads to improved dispersion stability.

The effectiveness of a high molecular weight polyol in improving the dispersion stability of a polymer / polyol depends (i) on the molecular weight and (2) its concentration in the polyol blend. The higher the molecular weight, the greater the improvement the dispersionBG stability, which is achieved with the same amount added will. The higher the amount of high molecular weight polyol used, the greater the improvement in the dispersion stability achieved. A significant improvement in the same can be achieved by adding only 5-45 wt .- ^ of a high molecular weight polyol. When choosing the amount and type of a high molecular weight polyol, however, other factors such as the effect on it should also be considered the foaming and foam properties are taken into account.

The polymer concentration in the polymer / polyol preparation according to the invention can be achieved by adding additional polyol to create the appropriate concentration of polymer for the desired end use can be set. So you can get polymer / polyol preparations

dilute to 4 % , produce with polymer concentrations of eg 20 % and eg / by adding further polyol; or the preparation can be used directly by the method according to the invention with a polymer concentration

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tration of 4 % can be produced.

The present invention also provides new polyurethane products that can be processed with the new polymer / polyol preparations getting produced; these new polyurethane products are obtained by reacting (a) a polymer / polyol preparation according to the invention, (b) an organic polyisocyanate and (c) a catalyst for the reaction of (a) and (b) to form the Polyurethane product, a blowing agent and a foam stabilizer usually also being used in foam production. Reaction and foaming can occur in any suitable manner, preferably by the one-shot process, although, however if appropriate, the prepolymer process can also be used.

The organic polyisocyanates suitable for preparing the polyurethane products according to the invention are organic compounds with at least 2 isocyanate groups; these compounds are known; they include the hydrocarbon diisocyanates, such as the alkylene cyanates and the arylene diisocyanates and the known triocyanates. Suitable polyisocyanates are, for example, 1,2-0iisocyanate-thane, 1,3-Oiisocyanatpropane, 1,2-Oiisocyanatpropane, 1,4-Diisocyanatbutane, 1,5-diisocyanatpentane, 1,6-diisocyanathexane, bis (3-isocyanatopropyl) ether, Bis (3-isocyanatopropyl) sulfide, 1,7-diisocyanatheptane, 1,5-diisocyanate-2,2-dimethylpentane, 1,6-diisocyanate-3-methoxyhexane, 1,8-diisocyanatoctane, 1,5-diisocyanate-2,2,4-trimethylpentane, 1,9-diisocyanate nonane, 1,10-diisocyanate propyl ether of 1 *, 4-butylene glycol, 1,11-diisocyanatundecane, 1,12-diisocyanatodecane, bis (isocyanathexyl) sulfide, 1,4-diisocyanatobenzene, 2,4-diisocyanattoluene, 2,6-diisocyanattatylene,

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1,3-diisocyanate-o-xylene, 1,3-diisocyanate-m-xylene, 1,3-diisocyanate-p-xylene, 2,4-diisocyanate-i-chlorobenzene, 2,4-diisocyanate-initrobenzene and 2,5-diisocyanate-1-nitrobenzene, 4,4'-diphenylmethylene diisocyanate, 3,3 · -Diphenylmethylene diisocyanate and polyraethylene-poly (phenylene isocyanate) the formula:

NCO

in which χ has an average value of 1.1-5 (preferably from 2.0-3.0), and mixtures thereof.

The catalysts suitable for preparing the polyurethanes according to the invention are: (a) tertiary amines, such as bis (dimethylamino-ethyl) ether, trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylbenzylamine, N, N -Dimethylethanolamine, N, N, N ¹ , N'-tetramethyl-i ^ -butanediamine, triethanolamine, 1,4-diazabicyclo- ^ 2.2.27-octane, pyridine oxide, etc .; (b) tertiary phosphines, the trialkylphosphines, dialkylbenzylphosphines, etc .; (c) strong bases such as alkali and alkaline earth metal hydroxides, alkoxides and phenoxides; ; (d) acidic metal salts of strong acids such as ferric chloride, stannous chloride, stannous chloride, antimony trichloride, bismuth nitrate and chloride, etc .; (e) Chelates of different metals, (let them e.g. from acetylacetone, benzoylacetone, trifluoroacetylacetone, kthylacetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetonimine, bis-acetylacetonealkylenediimines, salicylaldehydeimine etc., with the different metals, uiie Be, Mg, Zn Cd, Pb, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, Ni, or ions such as

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₂ ⁺ " ¹ ", U0 * ⁺ , etc. can be obtained; (f) Alcoholates and phenates of various metals, such as Ti (OR) ₄ , Sn (OR) ₄ , Sn (OR) ₂ , Al (OR) ₃ etc., where R stands for alkyl or aryl, and the reaction products of alcoholates with carboxylic acids, 6-0iketones and 2- (N, N-dialkylamino) alkenols, such as, for example, the known chelates of titanium obtained by these or equivalent processes; (g) Salts of organic acids with various metals, such as alkali or alkaline earth metals, Al, Sn, Pb _1x Mn, Co, Ni and Cu, including, for example, sodium acetate, potassium laurate, calcium hexanoate, stannous acetate, stannous octoate, stannooleate, lead octoate, metallic dryers, such as manganese or cobalt naphthenate, etc .; (h) organometallic derivatives of tetravalent tin, trivalent and pentavalent As, Sb and Bi, and metal carbonyls of iron and cobalt.

Particularly noteworthy organotin compounds are dialkyltin salts of carboxylic acid, such as dibutyltin diacetate, dibutyltin dilaurate, oibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, Dibutyltin bis (4-methylaminobenzoate), dibutyltin bis (6-methylaminocaproate) etc. Furthermore, a trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide or dialkyltin dichloride can also be used be used. Such compounds include, for example, trimethyltin hydroxide, Tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltinbend (isopropoxide), Oibutyltin bis (2-dimethylaminopentylate), Dibutyltin dichloride, oioctyltin dichloride, etc.

709852/1162

The tertiary amines can be used as primary catalysts to accelerate the reaction between reactive hydrogen and isocyanate or as secondary catalysts in combination with one or more of the metal catalysts mentioned above. Metal catalysts or their combinations can also be used as accelerators without using the amines. The catalysts are used in small amounts, for example from about 0.001-5 % _t based on the weight of the reaction mixture.

Is the product formed is a polyurethane foam, then this is obtained by using a "small amount of a Polyurethanblähmittels such as water, in the reaction mixture (eg etua 0.5-5 wt -.% Water, based on the total weight of the polymer / polyol preparation ), or by using blowing agents that are vaporized by the exothermic reaction, or by a combination of both methods. Suitable polyurethane blowing agents include halogenated hydrocarbons, such as trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dichloromethane, trichloromethane, 1,1-dichloro-i-fluoroethane, 1,1,2-trichloro-1,2,2-trifluoromethane, hexacycyclobutane, etc., another The class of blowing agents includes thermally unstable compounds which release gases when heated such as Ν, Ν'-dimethyl-N, N'-dinitrosoterephthalamide, etc. The generally preferred method of foaming to make flexible foams is to use water or a combination of Water plus a fluorocarbon blowing agent such as trichloromonofluoromethane. The amount of blowing agent used will vary with various factors such as that desired in the foamed product

709852/1162

Density.

According to the invention, small amounts, e.g. about 0.001-5.0 Wt .- ^, based on the entire reaction mixture, of a foam stabilizer, like a "hydrolyzable" polysiloxane-polyoxyalkylene block copolymer (e.g. the block copolymers described in US PSS 2,834,748 and 2,917,480) are used will. Another suitable class of foam stabilizers are the "non-hydrolyzable" polysiloxane-polyoxyalkylene block copolymers (e.g. US PSS 3,505,377, US patent application 888 067 dated December 24, 1969 and GB PS 1,220,471). These The latter class of copolymers differs from the abovementioned polysiloxane-polyoxyalkylene block copolymers in that the polysilox portion to the polyoxyalkylene portion through direct carbon-silicon bonds and not through Carbon-oxygen-silicon bonds are bound. These various polysiloxane-polyoxyalkylene block copolymers preferably contain 5-50 wt .- ^ polysiloxane polymer, wherein the remainder consists of polyoxyalkylene polymer.

The polyurethanes produced according to the invention can be used with success can be used for various purposes. For example, the present invention allows the production of polyurethane foams that can be suitably used in the slab foam field. The polymer according to the invention / Polyols are used to form polyurethane elastomers, in which relatively low molecular weight polyols are used to create the required rigidity must be used. The polymers / polyols according to the invention are also used to form polyurethane products suitable, especially for purposes where high load

709852/1162

load-bearing properties are required. The manufactured according to the invention Polyurethanes are suitable for all purposes in which conventional polyurethanes have been used, such as in manufacture of armrests, impact cushions, mattresses and automobile bumper bars.

In the present application the following terms are used: '

A / MMA / S means the weight ratio of acrylonitrile to methyl methacrylate to styrene.

A / 5 or A; S means the weight ratio of acrylonitrile to

Styrene.

All parts are parts by weight.

pll = pounds per linear inch, solids mean unreacted monomers.

TDI is a mixture of 80 % 2,4-tolylene diisocyanate and 20 %

2,6-tolylene diisocyanate.

TMSN is tetramethylsuccinonitrile (a decomposition product of

VAZO-64).

VAZO-64 or VAZO means 2.2 ^l -azo-bis-isobutyronitrile. TBPÖ is tert-butyl per-2-ethylhexoate.

All percentages and ratios are by weight -.% And weight ratios. The examples provided with numbers are according to the invention, the examples provided with letters are comparative examples not according to the invention. The polyols provided with letters are the lower molecular weight polyols, those with numbers

The polyols provided with them are those with a higher molecular weight. / · Poly A = polyacrylonitrile; Poly S = polystyrene

709852/1162

L.M.W, means lower molecular weight, H.M.W, means higher molecular weight.

The polyol ratios are based on weight and give the percentage of low molecular weight polyol first and then the Percentage of the high molecular weight polyol.

The calculated hydroxyl number given in the tables of the examples s are based on the calculated total polymer content and the hydroxyl number of the base polyol.

The light transmission data was obtained using light at a wavelength of 500 millimicrons, the polymer / polyol was in a 0.01- ^ iger dilution in a clear solvent

Polyol i = polypropylene oxide-polyethylene oxide-polyol made from propylene oxide and ethylene oxide and an 80/20 weight mixture of sorbitol and glycerin with a theoretical number average molecular weight of about 10800 and a hydroxyl number of about 28. The alkylene oxide units were mainly present in blocks, and the End units were practically all ethylene oxide units, ie the ethylene oxide was used to "cap" the polyol. The polyol contained about 8% by weight of ethylene oxide based on the total weight of the polyol.

Polyol Ü = polypropylene oxide triol, made from propylene oxide and glycerine with a theoretical number average molecular weight of about 6000 and a hydroxyl number of about 28.7,

709852/1162

Polyol'I ti = polypropylene oxide-polyethylene oxide triol, made from propylene and ethylene oxide and glycerol with a theoretical number average molecular weight of about 6000 and a hydroxyl number of about 26.1. The alkylene oxide units were mainly present in blocks and the end units were virtually all ethylene oxide units, that is, the ethylene oxide was used to cap off the triol. Based on its total weight the triol contains about 14 wt -.% C ₂ H ₄ O.

Polyol A = tripropylene glycol. Polyol B = dipropylene glycol

Polyol C to F = polypropylene oxide diols, made from propylene oxide and dipropylene glycol with a thaxetic number average molecular weight and the hydroxyl number from the following table:

Polyol

Polyol G = polypropylene oxide triol, made from propylene oxide and glycerine with a theoretical number average molecular weight of about 3000 and a hydroxyl number of about 55.4.

Polyol H = polypropylene oxide-polyethylene oxide triol, made from propylene oxide, ethyl oxide and glycerine with a theoretical number average molecular weight of about 3000 and a hydroxyl number of 56.4. Virtually all of the ethylene oxide units were internal, ie not in the form of end units.

Based on its total weight, this polyol contained approximately

709852/116 2

M.W. OH number 400 254 700 150.5 1000 112.1 2000 55.95

8% by weight of C ₃ H ₄ O.

POJyoi'3's polypropylene oxide-polyethylene oxide triol, made from propylene oxide, ethylene oxide and glycerine with a theoretical number average molecular weight of about 360Q and a hydroxyl number of about 46.7. Virtually all ethylene oxide units were inside "that is, not in the form of terminal units, based on its total weight of the polyol contained about 14 wt -. ?.

Pojyol K = polypropylene oxide-polyethylene oxide triol, made from propylene oxide, ethylene oxide and glycerine with a theoretical number average molecular weight of about 2700 and a hydroxyl number of about 62.14. tactically all ethylene oxide units were inside; the polyol contained about 8 wt .- ^ C ₂ H ₄ O ₁ based on its total weight.

Polyol L = polypropylene oxide-polyethylene oxide triol, made from propylene oxide, ethylene oxide and glycerine with a theoretical number average molecular weight of about 3400 and a hydroxyl number of about 49. Virtually all of the ethylene oxide units were inside as successive blocks; the polyol contained 10% by weight of # C ₂ H ₄ O based on its total weight.

709852/1162

Filterability

The preferred preparations according to the invention are practically free of polymer particles with a diameter greater than 30 microns The preparation meets this criterion if it is more than 99% by weight pass the same through a 150 mesh sieve and a 700 mesh sieve in succession in the following test · A 470 g sample of the test preparation is used to reduce the viscosity effect with 940 g

Dilute anhydrous isopropanol and pass the diluted sample through

2 and then a 150 mesh square sieve 15.5 cm

great
passed through an also / 700 mesh screen. (The screens are cleaned, dried and weighed prior to testing.) Then they are washed with isopropanol to remove any polyol, dried and weighed. The difference between the final and initial screen weight is the amount of polymer not going through the screens. The 150 mesh screen is square mesh with an average mesh opening of 105 microns and is a "standard Tyler" square 150 mesh screen. The 700 mesh screen is made of "Dutch twill ¹ * fabric

with average rresh openings of 30 microns and is in Bulletin 46267-R of the Ronningen-Petter Company, Kalamazoo, Mich ·, described,

Centrifugable solids

The polymer / polyol preparation is about 24 hours at etiaa 43000 rpm and 1470 radial centrifugal force "g" centrifuged. then • Invert the centrifuge tube and allow it to drain for 4 hours. The non-flowing cake remaining on the bottom pipe is expressed as the weight of the original weight of the test preparation specified.

709852/1162

Clear layer before emptying

The polymer / polyol preparation is placed in a small test tube and centrifuged for about 24 hours. The liquid in the test tube is then observed and the height of the upper clear layer is measured. This height is given as a percentage of the liquid height in the tea pipe.
Example 1 to 37 and A to F D _v ie Examples 1-37 and AF were continuously in a stirred tank reactor 550 CCRO-performed "fitted with baffle plates and a rpm at BOO driven stirrer. The feed components were continuously pumped into the reactor after passing through an on-line mixer to ensure complete mixing of the feed components prior to entering the reactor. The internal reactor temperature was ^{controlled to 1 0} C. by heating or cooling the reactor in a controlled manner from the outside. The product from the reactor flowed out through a back pressure regulator (this was adjusted to give a residue of 0.7 atm in the reactor). The product then flowed through a water cooled tubular heat exchanger to a receptacle. Shares the crude product was stripped under vacuum at 2 mm Druch and 120-130 ⁰ C. for testing. Conversions were determined from gas chromatographic analysis of the amount of unreacted monomers present in the crude product prior to stripping.

The experimental conditions and results of the above examples are shown in Tables I-VII below.

709852/1162

Table I. example 1 Polyol mixture A / I Received by N.M. to H.M. polyols 80/20 Reaction temp .; ⁰ c. 125 Veruieilzeit; min 12 VAZO in charge .; Geui.-jG 0.5 Monomeres + UAZO in charge .; Geui .- # 20.08 A / S in charge 78/22 Polyol feed schui .; g / h 2284 Feeding tasted by Mon. + UAZO; g / h 574 Product geuiicht; g / h 2842

Material compensation; % 99.44

remaining acrylonitrile; % 4.82

Styrene; £ 0.33

TMSN; % 0.17

Conversions; Acrylonitrile; % 68.64

Styrene; % 92.39

combined; % 73.86

Poly A im Prodi.It.Balchn .; Gev> .-% 11.06

Poly S ^H »» "ι Geui.-ji 4.20 Polymer im Prodi.It.Bechn .; Geui .- ^ 15.26 Product characteristics Brookfield Visc.B. 25 ° C; cps 257

calculated hydroxyl number; mg KOH / g 400.65

Light transmission; % 62.5

Filtration handicap

150 mesh sieve; % Passage 100

Solids on sieve; ppm 1

700 mesh sieve; Time in see 112

% Passage 100

Solids on sieve; ppm 6

centrifugal fixed; stripped; Gbvi .-% 11.14

clear layer before emptying; fL 6th

BI

80/20

123

12th

0.5

20.35

78/22

2246

574

2808

99.57

5.06

0.30

0.15

67.47

93.16

73.12

11.04

4.30

15.34

400

571.33

57.5

100

146 100

13.78 6

Acrylonitrile and styrene in a weight ratio of 78/22 became an 80/20 Ceuiicht mixture of 1,4-butanediol with UAZO and polyol I added. The UAZO carried the load

709852/1162

Concentration of 0.5 wt -.%, And the initial monomer plus VAZO-content 20.07 wt .-% The feed rate of the polyol was 2270 g / hr, the monomer and the VAZO-feed 570 g / hr. The product was obtained at a rate of 2836 g / h, the material balance was 99.86 %. However, this product settled in layers overnight, which shows the effect of the incompatibility of the polyols.

709852/1162

example
Polyol mix.
Relative to NM to HM

Polyols
Reaction stem .; ⁰ C.

Dwell time ₍ t; min VAZO in broom. #

Monom. + VAZO in
Broom.; Weight-i

A / S in complaint.
^ Polyol coating
<o speed .; g / h

»Monom. + VAZO coating -
^ speed; g / h

^. Product-
-"weight; g / h
- * Mater.aasgl .; g / h
2 remainder of acrylonitrile; £
Styrene; $
IMSN; i
Conversions
Acrylonitrile; $
Styrene; i
konb .; K>
Poly A in Prodi
according to calculation; Gw. - £

Poly S in Prod. It.
Calculate .; Wt .- <
Polymer in Prod.
It. Calc .; Wt .- ^

C / I
80/20

125

12th

0.5

20.34
78/22

2256
576

2820
99.58

3.14
0.40
0.19

79.8
90.88
82.23
12.81

4.11
16.92

Table II

4 5 6 7

C / I D / I D / I D / I D / I

90/10 68/32 75/25 80/20 90/10

125

0.5

08/20

2292 576

2860 99.72

3.07 0.35 0.16

79.97 91.90 82.59 12.66

4.10 16.76

10 11

ζ / ι "Wi Ί7ϊ

80/20 80/20 80/20

x20 120 120

IX.

Wi

80/20
120

120 120

0.5 0.5 0.5 0.5 0.4

20.67 20.6 20.49 20.20 19.57

0.46 0.53
23.34 27.13

2218 578

2789 99.75

2.36 0.39 0.21

85.03 91.23 86.40 13.76

4.16 17.92

2232 579

2811 100.0

2.53 0.36 0.20

83.86 91.86 85.62 13.54

4.18 17.72

2238 577

2802 99.52

2.58 0.41 0.20

83.54 90.72 85.12 13.44

4.11 17.55

82.89 91.27 84.74 13.14

2752
98.99

82.8
89.92
84.37
12.78

3.91
16.69

2128
648

2744
98.85

2.54
0.42
0.16

85.93
91.76
87.21
15.81

4.76
20.57

2036
758

2778
99.43

2.47
0.41
0.18

88.16
93.03
89.23
18.84

5.60
24.44

0.4

16.96
50/50

2272
464

2724
99.56

1.53
1.10
0.18

81.59

86.77

84.18

6.94

7.37
14.31

0.4

20.24
50/50

2199
558

2739
99.35

1.74
1.14
0.18

82.57

88.58

85.58

8.44

9.05
17.49

0.4

20.45 40/60,

2194 ■ $ - 564

2748 99.62

1.45 1.86 0.23

81.98

84.59

83.55

6.80

10.53 17.33

Table II continued Example 3 _4_ 5 6 7 8 9 1Ό_ U_ \ Z_ 13_ 14 Product characteristics Visco. (Brookfield)

at 25 C; cps 280 207 620 512 4) 3 330 476 58.8 652 772 844 852

calculate hydroxyl

number; mgKDH / g 173.7;

* ° translucent-

2 speed; i 63.3 ....... ^

00 filter obstruction

t "150 mesh sieve

¹ ^ i passage 100

2 ^ solids on
_^ Sieve; ppm 3
σ> 700 mesh sieve
*"Time; sec 108
i sag 100

Solids on

Sieve; ppm 14 8 12 0 7 3 19 40 10 3 3 2

centrifugal

Solids; stripped

Weight έ 4.85 12.67 2.42 3.62 5.12 16.74 5.55 5.50 7.75 4.85 10.15 13.70

clear layer in front of ^ j

To empty; i 4 6 44 2 14 4 44 135κ>

ι OO K)

192.75 91.76 98.95 104.14 114.57 79.64 75.93 72.23 43.42 41.80 41.99 58.5 70.0 69.8 66.0 58.70 63.8 62.3 61.0 47.0 46.2 41.8 100 100 100 100 100 100 100 100 100 100 100 5 21 2 3 4th 11 12th 7th 7th 8th 3 109 190 190 150 120 184 148 132 210 224 185 100 100 100 100 100 100 100 100 100 100 100

Table III

O
CD
CO

example Polyol mix. G

Verh.v. NM to IM polyols 100/0

React.temp .; ⁰ C. 125 residence time; min 51 VAZO in description; Gw.jt 0.4 Monom. + VAZO in
Bosch .; By weight JfL 22.65

A / S in description 100/0

Polyol coating speed

g / h 2144

Monomer + VAZO coating

quickly .; g / h 628 product weight;
g / h 2769 material equal; $ 99.89 resti. Acrylonitrile; i 2.89 styrene; £ - TMSN; i 0.17 conversions
Acrylonitrile? i ⁸⁷ °

Styrene; i
combined;

PoIyA im Prod.lt. Calculate .; % By weight of Poly S in Prod. It. Calc .; Weight %

Polyol in Prod. It. Calc .; Weight-4

87.0 01/20

-13L

G / II

85/15 125 12 0.4

23.26 100/0

2111 640

2743 99.70

4.19

0.15 81.73

81.73 19.51

16 G / I

80/20 125 12 0.4

23.37 100/0

2102 641

2736 99.74

3.80 0.15 83.5

83.5 19.94

17 18 19

Η / ΙΠ H / III G / III

B 20 21

G G / III G / III

- »100/0 85/15 85/15

125

18th
0.58

12 0.4

34.29 34.29 38.36 78/22 78/22 70/30

1828 1133 1784

705

1028

20.01 19.51 19.94

2750 1825 2796

98.85 99.29 99.43

2.62 1.89 2.41

0.40 0.24 0.46

0.17 0.23 0.17

90.20 93.63 90.53

94.70 97.13 95.78

91.19 94.40 92.10

24.59 28.20 23.59

7.28 8.25 10.70

31.87 36.45 34.29

12th
0.55

12th
0.55

18th
0.61

22nd

G / III G / III G / I G / I

85/15 85/15 80/20 80/20

36.42 36.19 40.60

78/22 78/22 78/22

1784 1084

1012 741

2776 1815

100.18 99.28 99.45

2.29
0.35
0.24

91.85

95.58
92.67

26.41

7.75
34.16

2.15
0.28
0.24

92.32

96.45
93.23

26.32

7.75
07/34

1.58 0.21 0.23

94.97

97.63 95.55

30.20

8.76 38.96

18 18 12

0.50 0.50 0.5

42.09 46.06 20.66 20.36

78/22 78/22 40/60 33.2 / 66.8

1073

780

2200 2200

573

1850 1710 2760 2756 99.84 94.89 99.53 99.30

2.27 0.32 0.21

1.09 1.14 0.20

J.05 2.25 0.23

93.01 reactor 86.54 84.18

96.50 amplified - 90.62 83.17

93.78 attempt 88.99 83.50

not

31.0 ended 7.14 5.75

9.07. 40.07

11.21 11.47 18.35 17.22

Table III continued Example £ 2! 5_ i6_ I £ _ IS ^ 19_ JJ 20_ 21_ Q__ Ό_ 22_ Product characteristics Brookfield visc.

b. 25 ⁰ C; cps 2004 2320 2780 2428 3200 3000 3532 2580 4430 6040 1264 1280

calculated Hydroxy I number;

mg KOH / g 45 41.5 40.34 35.56 33.17 33.85 36.60 33.96 ^ 31.45 30.87

Translucent '"

l &ssigkeit; % - 58.5 57.5 54.8 54.0 59.0 57.5 64.7

^ j Filtration hindrance? ο ISO mesh sieve

* P % Passage

(J ₁ solids on

N) sieve; ppm

* ■ * »700 mesh sieve

_k time; see σ> % passage · ° solids

Sieve; ppm ² * 10 12 8 8 18 28 10 30 188 centrifu ^ able
Solids, stripped
Oew.-i 19.44

clear layer before emptying; i 6

100 100 100 100 100 100 100 100 100 100 20th 4th 9 8th 6th 6th 4th 20th 10 14th > 1200
75.5 182
100 240
100 156
100 160
100 650
100 600
62.12 174
100 600
48.94 300
8th

41. 16 41. 73 40. 0 50. 0 100 100 8th 3 217 243 100 100

15th .71 22nd .28 5 .27 5 .94 8th .39 8th .07 S. .10 8th .24 17th .37 6th .25 14th 1
V. .01 > O 4th 4th 2 2 2 . - 2 2 • 2 2 2 2 NJ
CX)
NJ
CX) j
α

example Polyol mixture

Ratio of N M to HM polyols; Weight-i

ο reaction temperature; C.

Monom. + VAZO in charge .; Öew.-jb A / S in charge .; Weight-i

Polymer im Prod. It. Calc; Weight ί

ο Brookfield Viscose, at 25 C; cps

centrifuged. Solids, stripped; Weight-i

Pilgrimage obstruction

150 mesh sieve; $ 700 mesh sieve; i passage

Example 27 to 30

In these examples, a polyol mixture of 85 wt. %
Polyol K and 15 wt -.% Polyol III used. The reaction temperature was 125 ⁰ C. and the V / erweilzeit 12 minutes. The remaining conditions and procedures are listed in Table V below, and the general procedures are described in the examples above.

24 25th 26th Ι / Π J / II J / III 85/15 85/15 85/15 125 125 125 20.18 23.1 20.2 40/60 40/60 40/60 ·. 17.34 20.29 17.36 1460 1816 1620 06/10 14.72 10.14 100
100 100
100 100
100

709852/1162

Table V example

VAZO in charge; Oew, - £ Monomeree + VAZO in charge; A / S In Charge Polyol Charge Speed; g / h monom. + VAZO feeding speed; g / h product weight; g / h material compensation; 1 » residual acrylonitrile; £ styrene; %

TMSN; i
Conversions; Acrylonitrile; % Styrene; i

combined; ί

Poly A in Product It. Calc ·; Oew .- ^ Poly S in Product It. Calc; % By weight of polymer in the product according to calculation; Wt .- ^

Products in their own right

Brookfield viscosity at 25 ⁰ C; cps calc. hydroxyl number; mg KDG / g light transmission; % Filtrierbeh inde run g 150 mesh sieve; ί passage

Pesticides on sieve; ppm TOO mesh screen; Time, sec i passage

Solids on sieve; ppm «Entrifugierb. Solids, stripped; Wt .- * clear layer before emptying; i

28 29 30

0.4 0.43 "- 0.45 0.43 32.51 34.65 36.51 June 35 78/22 78/22 78/22 70/30 1877 1833 1772 1815 904 972 1019 980 2776 2794 2783 2791 99.82 99.61 99.71 99.86 2.79 2.67 2.63 2.45 0.37 0.36 0.35 0.45 0.17 0.17 0.21 0.20 88.88 90.04 90.68 89.91 94.77 95.23 95.60 95.67 90.17 91.18 91.76 91.67 22.99 24.89 26.30 22.45 6.91 7.43 7.82 10.24 29.90 32.32 December 34 32.69 2080 2464 2840 2580 40.01 38.63 37.60 38.42 57 57 54 100 100 100 100 29 27 11 16 198 192 194 191 100 100 100 100 6th 9 31 6th 6.11 7.19 8.71 11.14 4th 2 2 4th

N) OO N) OO

example Mixed polyols Vernältn.v. NM to HM polyols Reaction temp .; ⁰ C. Residence time; min VAZO in Beschik .; Wt .- ^ Monom. + VAZO in Bewchick .; A / S in charge Polyol feed speed; g / h Monom. + VAZO loading speed; g / h Product weight; g / h

Material compensation; ί residual acrylonitrile; ί styrene; 7 »TiISN; i

Conversions; Acrylonitrile; * Styrene; % ■ combined; &

Poly A in Product It. Calculate; Weight-5t Poly S in the product It. Calc .; Weight .- <polymer in the product It. Swrechn.r Gew .- ^

Product features

Brookfield visc. at 25 ⁰ C; cpa calculated hydroxyl number; mg KOH / g light transmission; % Filtrierhinderuni

150 'mesh screen; i passage

Solids on sieve; ppm TOO mesh screen; Time, see

ί passage

Solids on sieve; ppm »Entrifugierb. Solids, stripped; Wt. -4 clear layer before emptying; H>

Table VI 31 32 33 34 35 E. j7i J7i J7i _ J7i j7i J 80/20 80/20 80/20 80/20 80/20 100/0 125 123 120 120 120 100 12th 12th 12th 12th 12th 12th 1.3 • 1.3t 1.3 1.3 1.3 1.3 21.21 21.58- 21.70 20.86 21.53 21.64 30/70 25/7 20/80 30/70 25/75 30/70 2194 2180 ..... 2165 2216 2200 2220 S90 600 ·. ·. , 600 584 603 613 2768 " 2770 2753 2795 2772 , 99.5 99.64 99.56 99.82 98.89 1.02 0.97 J..03 1.11 1.14 ■ attempt 2.23 3.43 ' 5.53 2.36 3.67 • · not loading 0.61 0.62 0.62 0.61 0.63 · ■ ■ ends; 83.01 80.92 74.84 81.14 77.46 reactor 84.08 77.51 66.22 82.82 : 76.04 ■ 'violated 83.76 78.37 67.94 82.31 76.45 5.13 4.29 3.27 4.94 * 4.12 "12.13 12.34 11.56 11.78 11/12 J.7.26 16.63 14.83 16.72 16.23 / ■ * '
1508 1560 1496 2072 1344 35.8 07/36 36.85 36.03 36.25 41 47 - - —— 100 100 100 100 100 16 19th 22nd 22 51 350 600 400 1200 ' 600 14.33 23.5 0.33 36.03 9.93 181 81 201.969 265 330 8.99 17.23 30.91 20.76 16.7 0 6th 76 2 6th

Table VII example Polyols Proportions from NM tu HM polyols Reaction ^temperature i 0 C. Residence time; min VAZO 'in charge .; Gev .- < Monon. + VAZO in charge .; Qew.-Jf

A / MMA / S

Polyol feed rate j g / h Monom. + VAZO feed speed j g / h Product weight; g / h Material compensation; i

remaining acrylonitrile; £ MMA; i styrene;

TMSN; ί conversions; Acrylonitrile; £

MMA; i

Styrene; combined; % Poly A in the product It. Calcnj Oew. ^ Ji Poly MMA in the Pnväukt It. Oew.-i polymer in the product It. Bereehn; Οβν.-ί

I. I / I 100/0 80/20 115 115 12th 12th 1.3 1.3 20.86 * ' 21.48 25/25/50 25/25/50 2306 "'' 2204 608 608 2808 99.86 1.47 attempt 1.52 not finished 1.99 reactor 0.38 vera pots _(i 71.08 70.1 80.42 75.5 3.8 3.74 8.6 16.14

I / I

80/20

115

1.51

24.71

5/16/77

2108

692

2792

99.7

1.55

1.68

2.03

0.42

73.36

71.12

82.55

77.44

4.4.9

4.36

10.12

18.97

Table VII continued

Example £ j36_ 37.

Product characteristics

-J Brookfield Viscose, at 25 ⁰ C. » cps

° calculated hydroxyl number; rag KOH / g

oo filter obstruction

J ^ 150 mesh sieves i Durohgang

^ Solids on sieve; ppm not finished 15 22 * *

_ »700 mesh sieve; Time, see. ~ ^ΛΛ ^

_ » I passage

°> solids on sieve; ppm

*** centrifuged). Solids, stripped; Weight ίδ clear layer before emptying; %

1736 1708 36.28 June 35 Attempt . 100 100 not finished 15th 22nd reactor 300 300 clogged 4.47 4.68 1047 4.68 14.12 15.89 0 0

-kl · -

- 43- -

6 β i s' ρ i el

38 to 48

In these examples, the polymer / polyols prepared in Examples 17 and 24-29 were compared with other polymer / polyols identified by "PP" and a number; these were: Pft-Ί = dispersion of a 50/50 acrylonitrile / styrene copolymer with a copolymer content of 1Θ % , produced in polyol 3 using VAZO catalyst with a hydroxyl number of 36.9 mg KOH / g.

PP-2 = 72% dispersion of acrylonitrile and 28% styrene with 27.2% Nischpolymerisatgehalt, in copolymerized polyol L using VAZO having a hydroxyl number of 36.7 mg KOH / g and a viscosity at 25 ⁰ C. of 2854 cps .

PPt3 = dispersion of 78 % acrylonitrile and 22 % styrene with 32.9 % copolymer content, copolymerized in polyol H using TBPO with a hydroxyl number of 37.5 mg KOH / g. Aiiiinkätalysator = A solution of 70 Geiu.- £ bis- (2-dimethylamino-8thyl) ether and 30 wt -.% Dipropylene glycol.

TDi = mixture of 80 Geui .- # 2,4-tolylene diisocyanate and 20 wt _# - S 2,6-tolylene diisocyanate.
Silicone surfactant j

Silicone superficial contact agent Π
Mix of

55 Cw% (CH ₃ J ₃ SiO

• Si-O-

.Si-O-

Si (CH ₃ )

and

45 Gw- ^ a mixture of

C ₄ H 0 (C ₂ H ₄ O) ₁₈ (C ₃ H ₆ O) _13? H (90% by weight ) and

^C 9 ^H 19 ^C 6 ^H 4 ^OlC 2 ^H 4 ^O] 10.5 ^{H (1} ° ^Ββ "·" ^

709852/1162

- 44 -

The following test procedures were used in the following examples applied:

Indentation load deflection

("indentation load deflection")

s ILO ASTH D1564-69

permanent deformation "

Tensile strenght "

Strain "

ReiQuiiderstand (tear resistance) ■ Air porosity

A foam sample 1.25 cm thick was placed between two pieces a flanged plastic tube 6.25 cm internal diameter pressed together. Then this structure becomes a component in an airflow system. The air enters at a controlled speed one end of the pipe, flows through the sample and kicks through a constriction at the rear end of the structure from «The pressure drop An inclined, closed tonometer is used to measure over the foam due to the narrowed air passage · A monometer end is connected to the upstream foam side, the other end is connected to the downstream side. The air flow on the upstream side becomes like this set that a differential pressure of 2.54 mm over the water Sample is maintained. The air porosity of the foam is expressed as units of air flow per unit area of the sample, namely in cubic feet / min / ft. .

Ee were low-density, flexible polyurethane foams from the polymer / polyols prepared according to the invention from Examples 17 and 24-29 and, for comparison purposes, from not according to the invention produced polymer / polyols. The foam formulation

709852/1162

ments are listed in Tables VIII, X and XI, where the amounts are given in parts by weight.

The foam formulations were learned in accordance with the following Polyurethane foams converted. The surfactant, the polymer / polyol and TDI were weighed into an 8-1 stainless steel baffle beaker and weighed for 60 seconds at 2000 rpm with two 6.25 cm 6-blade turbine stirrers (in a distance of 6.25 cm qn the shaft base) mixed. The stirring was interrupted for 15 seconds for degassing and continued for a further 5 seconds. After adding water and amine catalyst mixture was mixed for an additional 5 seconds. Then stannous octoate was added and mixed for an additional 5 seconds. The foaming one Mixture was poured into a paper-lined box measuring 60 60 χ 50 cm and the foam rise time was determined The foam was allowed to cure overnight at room temperature. The physical properties of the Foam measured on a 12 cm sample taken from the bottom of the top half of the foam pillow.

The physical properties of the foams were determined and are listed in Tables IX, X and XI.

709852/1162

Table VIII example

39

40

41

42

Polymer / polyol:

pp_1 100

Example 24
ι · 25
"26
Solids

Polyol 3 100%

Polyol II

Polyol III

water

Amine catalyst 0.10

Stannous octoate 0.20

if.fl.act.siliconwith.I 1 ° TDI 41.5

Index 105

Rise time; sec H ³

Comments: OK

100

17.34

85%

15%

100

outwardly OK
columns

100

20.29

85%

15%

100

20.29

85%

15%

no
Blistering

98
OK

100 17.36 85%

20th 0. 325 0. 30th 0 .275 15% 4th 41. 4th 41. 2 41 .2 0. 0.2
V 41. 41.4

102 OK

K) OO K) OO

O CO OO

example Physical · Properties

Density; pcf

Air porosityMt; ft ³ / min / ft ² rebound force; % "ball rebound"

ILD (lbs / 50 in ² )

25 %

⁶⁵ ί

25 % recovery; %

Load ratio

Tensile strenght; pel stretch; % Tear strength; pli

90 % permanent set; CD; % 1.76

39

1.73

6.2

41

1.77

6.8

42

1.77

86.1
42 74.2
42 79.
39 6th 87.3
42 55.5
110.5
61.6
1.99 55.5
104.0
59.3
1.87 62.
114.
57.
1. 0
8th
7th
85 58.3
106.8
58.7
1.83 18.0
128
2.50 18.2
144
2.45 20th
134
2. 0
66 18.8
133
2.89

6.1

Table X Example HIJ 43 44 Polymer / polyol

PP-2 100

PP-3 - 100 100

Example 17 "100 100

water

^ ³ amine catalyst

J? Stannous octoate ZI ob.fl.akt. Silicone agent I.

cn TDI (107 index)

> s. Foam rise time; sec

cd physical properties

** density; pcf 1.49 1.54 1.57 1.50 1.51

Air porosity; ft ³ / n »in / ft ² rebound ability; % "ball rebound ¹ * ILD (lbs / 50 in ² )

25 %

65%

25 % recovery; %

Load ratio

4.0
0.10
0.30
1.0
47.4
75 0. 25th 0. 30th 0 .30 0. 325 47.
114 5 47.
101 5 46
80 .8th 46.
74 8th

21.4 50.0 19th 8th 10.7 6.6 to 26th 23 24 26th 22nd 89.8 91.3 96 0 93.8 92.0 to 167.5 170.0 187. 5 170.3 171.0 OO 48.7 46.2 46. 0 45.4 46.3 ro 1.87 1.86 1. 95 1.82 1.86 OO

table'X Continuation

43

Tensile strengthipei
Strain; % 20.8
88 O Tear strength; pli 2.0 (D permanent deformation; 'C ^ i % 852/1 50 %
75 %
90 % 13.4
16.0
66.8 162

23.1
87

2.05

59.0

23.0
77

2.60

22.6
-

2.26

11

22.8

90

2.31

31. 2 17th .3 19th .1 39. 0 45 .2 41 .2 78. 0 82 .2 85 .6

OO KJ OO

Tabel'*!

Example Polymar / Polyol

PP-2

Example 17 27 28 29

water

Amine catalyst stannous octoate

Il
Il

O
(D
OO

ro ob.ri.akt. Silicone agent II ^ TDI (107 index)

- »polymer / polyol

Polyol 3

" H

"K

"III solids} % rise time see

Physical Properties

Density; pcf

Air porosity; ftV / rebound capacity .; % "ball rebound"

100

100%

27.2
65

1.41
25.0
29

45

100

47.3

85%

15%

31.9 66

1.44

14.4 27

47

48

48.0

85% -15% - 29.9 68

1.42 4.2 24

loo

47.7

32.3 65

1.44 8.8 27

100

47.5

34 .1 K>
-J 64 K) 1 .41 OO 3 .5 K) 22nd 00

Table XI fortaetzuno

ο co co

example

ILD (lbs / 50 In ² )

25 %

65 %

25 % recovery; %

Load ratios

Tensile strenght; psi elongation; % Tear strength; pll

90 % permanent recovery;

87.5 157.8 49.9 1.80

20.2 85
2.35

59.9

90.1 160.8 46.3 1.78

21.4 75
2.45

71.8

46

86.5 152.0 48.7 1.76

23.4 95 2.57

62.2

47

98.8 172.5 46.0 1.75

23.7 82 2.28

68.4

48

99.8 177.0 44.9 1.77

25.5 86 2.69

78.0

The data of Table X show that the polymers / polyols of the invention for the production of flexible foams with higher load-bearing properties, which can be used as carpet underlay, or solid polyurethane elastomers with higher modulus for use in the automotive industry Polymer / polyols made with lower acrylonitrile to styrene ratios are relatively non-staining while having a higher load bearing capacity, as can be seen from the data in Tables VIII and IX. It would have been expected that the addition of 15 % of a high molecular weight polyol to the foam formulation would reduce the load-bearing properties of the foam by possibly 10 % . In contrast, the data from the foam evaluation according to Tables VIII, IX and X show that, unexpectedly, there is no loss of the load-bearing foam properties. Examples 49 to 93 and L to O

Examples 49-93 and LO were carried out continuously in a continuous stirred tank reactor which was provided with baffle plates and a stirrer usually operated at 800 rpm. The feed components were pumped in for continuous reaction after passing through an intermediate mixer to ensure complete mixing of the feed components prior to entering the reactor. The internal reaction temperature was increased to 1 ° C. controlled by applying regulated heating or cooling to the outside of the reactor. The product from the reactor flowed through a back pressure regulating _device> from (this was adjusted so that a back pressure of 0.7 atm is in the reactor revealed). Then the product flowed

709852/1162

through a water cooled tubular heat exchanger to the product-receiving tank · Parts of the crude mm pressure and 120-130 ⁰ C. were vacuum stripped for testing at second The conversions were determined from the gas chromatographic analysis of the amount of unreacted monomers present in the crude product before stripping.

The experimental conditions and results of these examples are in the following Tables XII to XIX listed. The polyols used have been identified above. The following have also been identified Polyols used:

Poiyoi IV = polypropylene oxide-polyethylene oxide-polyol, made from propylene oxide and ethylene oxide and sorbitol with a theoretical number average molecular weight of about 12,000 and a hydroxyl number of about 27.87. The alkylene oxide units were mainly in blocks and the end units were virtually all ethylene oxide units, that is, these were used to cap the polyol. The polyol contains about 8.6 wt -.% Ethylene oxide units, based on the total Polyolgewischt.

Polyol V = polyol made of 65 wt -.% Propylene oxide and 35 wt .- / S ethylene oxide and sorbitol with a theoretical numerical average molecular weight of about 10 300 and a Hydroxylznhl of about 27.77. The alkylene oxide units were mainly in blocks and the end units were virtually all ethylene oxide units, ie 15% by weight of the ethylene oxide was used to cap off the triol. The polyol contains about 44 wt -.% Ethylene oxide units, based on total product weight ·

709852/1162. .,

example

Polyol mixture ratio from NM to HM polyols Reaction temperature; C.

Residence time; min VAZO in charge .; Gev.-i Monom. + VAZO in charge .; Gew.-i A / S in charge

Polyol feed speed; g / h

Monom. + VAZO loading speed; g / h

Product weight; g / h

Material compensation; ί

remaining acrylonitrile; i styrene; % TMSN; %

Conversions; Acrylonitrile; Styrene; % combined; %

* ■ ». Poly A in Prod. It. Calc .; Gew. - $ - »Poly S in Prod. It. Calc .; Weight ί - * Polymer in Prod. It. Calc .; Wt £ product properties Brookfield viscosity at 25 ⁰ C; Calculate cps. Hydroxyl number; mg KOH / g

Light transmission; % Filtration obstruction 150 mesh screen; % Passage

Solids on sieve; ppm 700 mesh screen; time, see

I passage

Solids on sieve; ppm centrifuged). Solids, stripped; By weight clear layer before emptying; i

- Tabel 49 50 51 52 M. N L. g7i Wi g7i g7i G / I G Ϊ 60/40 80/20 90/10 94/6 98/2 100/0 0/100 125 125 125 125 125 125 125 12th 12th 12th 12th 12th 12th 20th 0.5 0.5 0.5 0.5 0.5 0.5 0.5 20.19 20.35 20.59 20.10 June 20 20.57 20.66 50/50 50/50 50/50 50/50 50/50 50/50 50/50 2206 2208 2206 2210 2216 2216 1344 558 564 572 556 556 574 350 2738 2762 2776 2756 2768 2778 1688 99.06 99.84 99.73 . 99.64 99.85 99.57 99.6 1.43 1.41 1.46 1.50 1.50 1.51 1.14 0.907 1.02 1.06 1.04 1.07 1.13 0.675 0.259 0.21 0.22 0.23 0.22 0.27 0.226 85.62 85.85 85.47 84.76 84.69 85.02 88.73 90.88 89.76 89.46 89.43 89.08 88.79 93.33 88.25 87.80 87.46 87.09 86.88 86.90 91.03 8.63 8.74 8.81 8.53 8.51 8.76 9.11 9.17 9.13 9.22 9.00 8.95 9.15 9.58 17.80 17.87 18.03 17.53 17.46 17.91 18.69

1440

37.22 51.2

100

246 100 22 2.75

1184

41.47 47.8

100

178

100

4.31

1112

43.52 46.8

100

180

100

10

5.60

1012

44.64 46.0

100

11

216

100

33

7.03 4

1036

45.54 46.5

100 4

184 100 12

9.27

table XIII example Polyol mixture

Ratio of NM to HM polyols reaction temperature; ⁰ C. residence time; min

WZD in loading; -% monom. + VAZO in charge; Gew.-Jb

A / S in charge

Polyol feed speed; g / h monom. + VAZO loading speed; g / h Product weight; g / h

Material equalization, remaining acrylonitrile; %

Styrene; %
TMSN; %

Conversions; Acrylonitrile; % Styrene; % combined; %

Poly A in the Prod.ute Calc ·; Gew .- ^ Poly S in the Prod.laut Calc ·; % By weight of polymer in the product as calculated; Häften% Product intrinsically sc - weight.
Brookfield viscosity at 25C; cps calc. Hydroxyl number; mg KOH / g light transmission; % Filtration obstruction

150 mesh sieve; % Passage

Solids on sieve; ppm

700 mesh sieve; Time to see % passage solids on sieve; ppm

centrifuges solids, stripped; Weight clear layer before emptying; %

100/0

125

12th

1.2

22.89

100/0

2142

636

2740

98.63

3.56

0.50
83.79

83.79
18.82

800
91.40

100

296
900
36.5

533

57.98

46

E / III

90/10

125

1.2

22.43

100/0

2158

624

2774

99.71

2.78

0.49 86.93

86.93 18.99

18.82 18.99

1172

81.15

72.8

100

11

150

100

7th
20.36

70985.2 / 1162

table XIV

(D
OO
cn
ro

Example l FsiyoloiTs chung Proportions from NM to HM polyols Reaction temperature; C. Veriu hurry time; min

VAZO 'in charge; Gevi .-%

Monom. + VAZO leg feed; Geui .- ^ S

A / s in charge

Polyol feed schui .; g / h

Monom + VAZO loading-schu ».; g / h

Product suitability; g / h Material compensation; %

remaining acrylonitrile; %

Styrene; %

TMSN; %

Conversions; Acrylonitrile; % Styrene; % combined; %

Poly A in prod. According to calculation; Geui.-jG Poly S im Prod. According to calculation; Ze \ s> .-% polymer in the Prod. It. Calc .; # Product specifically chaften Brookfield viscosity at Calcd. Hydroxyl number; mg light transmission; % FiI handicap

15o mesh sieve; %

25 ° C .; KOH / g

cps

% Passage

Solid peat on sieve; ppm 700 mesh screen; Time; lake

% Passage

Solids on sieve; ppm solids stripped; Geu ».-%

To empty; %

centrifuged.
clear layer in front

54 55 56 h7i Wl ■■ _ « h7i 80/20 70/30 60/40 125 125 125 12th 12th 12th 1.60 0.75 1.1 32.11 32.78 33.33 40/60 40/60 40/60 1894 1876 1864 896 915 932 2786 2777 2790 99.86 99.50 99.78 1.28 1.41 1.30 1.41 1.86 1.45 0.70 0.34 0.58 89.53 89.05 89.94 92.31 90.37 92.52 91.20 89.84 91.49 11.25 11.80 11.94 17.40 17.97 18.42 28.65 29.77 30.36 2140 2572 2800 38.14 07/35 33.02 47.0 45.7 45.8 100 100 100 11 17th 2 300 176 277 11.33 100 100 35 11 16 15.71 12.60 10. 7Q 4th 2 2

hO OO KJ OO

57 58 59 Table XV 60 61 62 ■ ■ "» • 64 65 66 67 68 example h7iv k7iv- fr h7iv - h7i k7i- W W Polyol mixture
Ratio of NM to 80/20 HM polyols; 80/20 85/15 80/20 Wt %
Reaction temp .; C. 80/20
125 85/15 90/10 Dwell time 12th VAZO in broom .; Wt .- ^ 0. 8 30.76 Monom. + VAZO in 30.68 30.58 32.15 35/65 Feed .; Weight-i
A / S; Weight-i 30.39 31.0L 31.23 1922 98.48 Polyol charge, - 40/60 854 30.58 31.46 32.49 99.50 ^ eeschw.je / std
° monom. + VAZO loading 1935 1916 19 2 3 1880 2762 LCi I ΑΠ * - * £ * eschw .; g / h
"Product- 845 1937 1940 848 84 7 891 99.62 1913 (fAM 4 / * Vl t * (T / β + / ^ 2762 871 881 2733 2741 2743 1918 1926 1880 852 1875 ^ »Material compensation; % 99.35 2800 2812 98.88 98.95 98.99 1.32 845 884 905 2723 9 39 ~ * rest 99.71 99.68 1.71 2749 2786 2766 98.48 2800 _ Acrylonitrile; i 1.37 1.67 1.62 1.44 0.50 99.49 99.14 99.31 99.50 ^ Styrene; * 1.54 1.42 1.45 1.67 1.60 1.59 1.88 TMSN; i 0.42 1.47 1.69 0.44 0.37 0.35 87.48 1.38 1.35 1.45 1.83 1.79 Conversions 0.38 0.43 91.26 1.43 1.64 1.76 0.36 1.81 Acrylonitrile; 88.50 86.18 86.54 88.63 89.94 0.34 0.39 0.46 0.40 Styrene; i 91.39 88.28 88.12 90.79 91.13 91.63 84.58 combined; i 90.23 91.91 90.77 88.95 89.30 90.43 9.47 88.47 89.08 88.62 89.99 86.30 Poly A in Prod.- It. 90.46 89.71 92.04 91.15 90.79 87.83 90.76 Calculate .; Wt 10.80 10.66 10.66 11.47 18.35 90.61 90.32 89.9 3 88.98 Poly S in Prod. It. 10.99 11.08 * ' 10.55 Calculate .; Wt .- ^ 16.73 16.85 16.83 17.79 10.85 11.26 11.60 11.65 17.17 December 17 16.83 Kj 16.93 17.28 17.83 18.37 ^
to
OO
ro
¹ OO

Tabel XV continuation

O example 57 2 58 59 60 ■ 61 62. 62 64_ 65 54 46 66 £ 7 68 K) OO Polymer in prod.
Calculate .; Wt .- ^ 27.53 - · 28.16 28.20 27.51 ) ppm phenothiazines 27.49 29.26 27.82 27.78 28. 3 29.43 27.38 02/30 Oil Product features This is suspected at the beginning K)
1 OO ro Brookfield viscosity 2412 Φ OO at 25 ° C; cps 2160 2259 2584 2180 2576 2396 2000 2172 2552 2308 2976 • «Γ- calculated hydroxyl 35. co number;
mg KOH / g 36.73 37.44 38.44 40.22 41.49 35.86 36.59 36.85 46. 36.01 40.54 39.07 ft « Light through
nonchalance; i 46.5 47.0 53.5 44.5 50.0 46.0 49.8 45.0 49.8 47.0 59.8 -J FiIt ier disability ■ -> 150 mesh sieve; 100 96 * $, Passage 100 100 100 100 100 100 100 100 100 100 100 Solids on 25th Sieve; ppm 7th 4th 11 11 15th 6th 7th 12th 74 18th 14th 9 '■> 7DO mesh sieve; 407 Time; sec 524 600 1200 1200 749 1200 410 1200 24. 1200 1200 250 S. $> Passage 100 31 16.8 43.83 29.21 38.37 100 19 * 46.38 32.12 4.33 "S. Solids on 38 Sieve; ppm 14th 16 66 55 315 201 11 50 12th 160 35 329 centrifuged. Solids
stripped; Wt% 10.97 15.76 21.81 11.15 16.23 17.25 10.46 10.47 2 15.74 15.76 19.93 clear layer in front
To empty; i 2 4th 2 2 2 2 2 2 2 2 Polyol H was rated at 500 ppm Jonol and % stabilized ♦ Formation of germs / during <
("seerirj'O

O
(O
OO

example Polyol mixture Proportions from NM to HM polyols; Weight ί Reaction tea; C. Residence time; lake VAZO in total load .; Wt .- ^ Monom. + VAZO in Beschck .; Gev .-%

A / S; Weight-2

Polyol feed speed; g / h Monom. + VAZO loading speed; g / h Product weight; g / h Material compensation; %

residual acrylonitrile; i »

Styrene; %

TMSN; %

Conversions; Acrylonitrile; 1 » styrene; % combined;

Poly A in product according to calculation; Weight .- ^ t Poly S in Prod.lt.Balchn .; % By weight of polymer in product It. Calc .; Weight-Ä Product properties Brookfield viscosity at 25 ° Cj cps

calculate Hydroxy1 number; mg KOH / g light transmission; %

Table XVI 71 Ii 73 74 75 Il TfiS * 69 70 ^ ~~ t7l U / T h7iv π / χ 125 12th 1.51 1.60 1.2 1.40 1.52 1.60 1.58 1.2 1.40 30.48 32.33 24.22 ' 28.21 30.72 32.11 11/15 24.29 28.21 40/60 - 1923 1890 2121 2016- 1935 1894 1213 * 2094 1990 843 903 678 792 858 896 243 672 782 2754 2787 2778 2796 2772 2786 1444 2751 2760 99.57 99.78 99.25 99.57 99.25 99.86 99.17 99.46 99.57 1.33 1.25 1.31 1.28 1.26 1.28 - 1.29 1.27 1.61 1.51 1.72 1.53 1.50 1.41 - 1.71 1.51 0.64 0.65 0.59 0.60 0.65 0.70 - 0.62 0.62 88.59 89.85 85.88 88.11 80.29 89.53 - 86.11 88.21 90.78 91.83 87.64 90.53 91.50 92.31 - 87.72 90.65 89.89 91.04 86.94 89.56 90.62 91.20 - 87.08 89.68 10.59 11.37 8.16 9.73 10.74 11.25 7.2 ** 8.21 9.74 16.27 17.43 12.50 3 p.m. 16.50 17.40 11.41 ** 12.54 02/15 26.86 28.80 20.66 24.73 27.24 28.65 18.69 ** 20.75 24.76

1764

40.0
42.0

2020

38.89
44.2

2200

37.86
46.5

1416 1760 1984

42.41
36.8

40.24
46.2

38.90 45.8

2140

38.14 47.0

1432

"'S * ³

Table XVI continued Table XVI continued

ii 70 71

21 73

74 75

Example
Filtration obstruction

150 mesh sieve; % Through

Fixed on a sieve; ppm

700 mesh sieve; Time, sec

% Passage

Fixed on a sieve; ppm

centrifugeb. Solids, stripped wt -.% Clear layer before Ausl.j%

The polyol H was with 1500 ppm ionol, 150 ppm phenyldiieodecyl phosphite and 50 ppm Phenothiazine stabilized and had a hydroxyl number of about 59.5. ♦ contained 49.01 Geu / .- £ toluene in the charge ♦ * toluene-free basis

76

76S *

100
7th 100
2 100 100 100 100 100 100 9.57 200
100
7th 219
10 0
6th 597
100
7th 5
600
22.5.
⁴⁰ ' 29
216
100
15th 27
220
100
20th 9
1200
41.16
24 11
300
11.33
35 778
300
0.85
9161 3.61
2 9.23
2 11.23
2 13.17
2 4.53
2 13.78
2 12.61
2 15.71
4th 34.49
40

K) OO K) OO

O (O OP

Example poly blend

Ratio of NM to HM polyols; . Wt -% reaction temperature; C. Fast delivery time; min VAZO in total load ·; Geur, -.% Monom. · «- Vazo in charge ·; Geu; .-% A / S; Geiu .-? A

Polyol charge.geechiu .; g / h monom. + VAZO Beschick.geschuu; g / etd product weight; g / h material compensation; % re3tl. Acrylonitrile; % Styrene; % TMSN; %

Conversions; Acrylonitrile; % Styrene; % combined; %

Poly A in Prod. It. Calc ·; Geiu .- ^ Poly S im Prod. It. Calc .; Geiu.-V Polymer im Prod. It. Calc .; Geiu.-Ji ProdukteiQens' adhere to Brookfield viscosity at 25 C .; Calculate cps. Hydroxyl number; mg KOH / g light transmission; % Filtering obstruction

150 mesh sieve; % Passage solids on sieve; ppm

700 mesh sieve; Time; see % passage

Solids on sieve; ppm

centrifugeb. Solids, stripped; Geu »,% clear layer before emptying; %

Polyol H had rji ₀ same? Hyriroxyl number as stabilized

tebtli 78 21 80 Ii 82_ 11 77 ϊΓ7ΐν ... 80/20 - 0.8 0.7 0.6 0.5 0.4 0.3 1.51 29.85 30.13 30.21 29.89 30.34 30.38 30.48 2002 1978 1968 1921 1924 1932 1923 852 853 852 819 838 84 3 84 3 2839 2807 2806 2730 2748 2760 2754 99.48 99.16 99.50 99.63 99.49 99.46 99.57 1.39 1.38 1.39 1.77 1.84 1.99 1.33 1.69 1.69 1.67 2.33 2.60 2.62 <& 1.61 0.40 0.34 0.29 0.29 0.19 0.18 * Λ 0.64 88.10 88.37 88.32 85.0 84.71 83.55 88.57 90.36 90.51 90.64 86.83 85.60 85.56 90.78 89.45 89.65 89.71 86.10 85.24 84.75 89.89 10.57 10.73 10.79 10.42 10.62 10.54 10.59 16.26 16.49 16.62 15.98 16.09 16.18 16.27 26.83 27.22 27.41 26.40 26.71 26.72 26.86 2028 2018 2100 2040 2000 2008 2020 38.90 38.69 38.60 39.13 38.97 38.96 I. 38.89 45.0 44.2 45.5 43.5 44.3 45.0 44.2 100 100 100 100 100 100 100 37 20th 15th 3 4th 6th 7th 472 1200 454 250 2 70 256 Ty 597 100 100 100 100 100 ioo --J 100 33 28 11 2 4th 4 ro
oa_ 7th 14.35 14.40 15.35 May 15 May 18 11.23 2 2 2 3 2 4 '£> 2

ih Table XVI and was in the same '..' way

table Mt ti

_O
to
oo
cn

HM

Pulyols;

Example l Polyol coating Ratio of WM to Reaction temperature; Lingering time min UAZO in charge .; Ge \ i>, -% Monom «+ VAZO in charge ·; Geui.-Ji

A / S; Geiu .- ^

Polyolbe'schick.geschu /. ; g / h Monom. + UAZO Beschick.gescniu ,;

Product suitability; g / h

Material compensation; %

remaining acrylonitrile; %

Styrene; %

THSN; %

Conversions; Acrylonitrile; % Styrene; % combined; %

Poly A in Prod. It. Calc .; Poly S in Prod. It. Calc .; Polymer im Prod. It. Calc ·; Product properties Brookfield viscosity at calc. Hydrojcylzr.hl; mg light transmission; % Fi Itration treatment indu ng
150 mesh sieve; %

g / h

25 ⁰ C; KOH / g

cps

700 mesh sieve;

centrifuged

Passage

Solids on sieve; ppm time, see % passage

Solids 3Uf sieve; ppm solids stripped; %

g, g

clear layer before emptying; %

84 85 86 IZ 88 89_ 90 77 ν ϊΓ7τ H / IV
80/20 80/20 80/20 80/20 80/20 80/20 80/20 125 125 125 125 125 125 125 12th 12th 12th 12th 12th 12th 12th 0.80 1.3 1.51 1.71 1.92 0.47 0.60 30.39 21.17 24.78 28.06 31.43 28.20 32.17 40/60 40/60 40/60 40/60 40/60 40/60 40/60 1935 2212 2076 2030 1920 2021 1948 845 594 684 792 880 794 924 2762 2774 2740 2788 2796 2803 2850 99.35 98.86 99.27 99.79 99.86 99.57 99.23 1.37 1.14 1.31 1.15 1.31 1.48 1.54 1.54 1.41 1.42 1.19 1.20 1. 76 1.81 0.42 0.67 0.82 0.79 1.06 0.26 0.30 88.50 85.83 86.02 89.22 88.91 86.72 87.90 91.39 88.31 89.90 92.56 93.23 89.4 7 90.51 90.23 87.30 88.35 91.23 91.51 88.36 89.4 7 10.80 7.01 8.24 9.64 10.79 9.95 11.49 16.73 10.82 12.92 3 p.m. 16.97 15.39 17.74 27.53 17.83 21.16 24.54 27.76 25.34 29.23 2160 1720 1976 2280 2504 1840 2516 36. 73 41.11 39.44 37.70 36.14 38.10 36.11 - 45.5 41.0 45.0 38.2 48.0 49.8 100 100 100 100 100 100 100 7th 7th 7th 28 31 53 6th 524 600 600 270 500 201 1200 100 N3 8th 19.83 100 5.5 100 96.6 14 ^ 319 61 26th 1127 9 35 10.97 ^ 6.94 7.99 9.61 12.12 11.58 14.74 2 CX) 3 2 2 2.5 4th 4th

example
Polyol mixture

Proportions from NM to HM polyols; . Wt -% reaction temperature; C. UAZO in total batch; Geui.-ji stabilizer; Geui .- / 2 in charge Monom. + VAZQ in charge .; Geu /.-$ Ratio. from acrylonitrile to styrene; Geui.-jS Polyol + Stabilis.-Besch ick.geschiü. ; g / h (3) monom. + VAZO Beschick.geschuj .; g / h product weight; g / h material compensation; % residual acrylonitrile; % Styrene; % TMSN; %
Conversions; Acrylonitrile; %

Styrene; %

combined; (case?)

Total Poly A in Prod. It. Total Poly S in Prod. It. Total polymer in Prod. It. properties Brook field viscosity at

calculate Hydroxyl number; mg

Filtration obstruction

150 mesh sieve;

Calculate .; Calculate .; Calculate .;

Wt % wt % 6 wt% 6
9,

25 C KOH / g

cps

700 mesh sieve;

centrifuged

% Passage solids on time, see % passage solids on solids;

Sieve; ppm

Sieve; ppm

G
Light transmission; % 11

J / I1I
85/15
120
0.4

19.9
40/60
(A)
(5)

0-0,
, 09-0,
, 05-0,

01 (6)
12 (6)
13 (6)

81-7.29 (6)
37-10-.5K6)
18.2

ι ·

1638
35

100

15th

391

100

IA

10.3

50

11

K / 111

85/15

125

0.8

5.62 (1)

32.55

/.0/60

1898

916

2806

99.71

1.23

1.30

0.41

90.3 «

20th

06

8th

23

93
92
11
18th

01/30

2336
36.75

100

28

1200

67.66

79

2.82

93

k7iii

85/15 125 0.64 5.27 (2)

29.8

40/60

1946

826

2752

99.28

1.44

1.73

0.28

87.

90,

89

11 17 29

18 21 51 75 26

1928 37.38

100

49

800

100

12th

2.43

Footnotes to Table XIX:

(1) The stabilizer was prepared by reacting the reaction product of 2 moles of polyp; gpylene oxide-butanol adduct with a molecular weight of about 2500 and 1 mole of TDI in toluene, which is chemically attached to a copolymeric anchor part made of acrylonitrile and styrene in a weight ratio of 30:70 according to Example 247 of US application Ser.No. 752 818 of December 20, 1976 bound was

(2) The stabilizer was prepared from the reaction product of propylene oxide and glycerin having a molecular weight of 6000 and a copolymer anchor part made of acrylonitrile and styrene in a ratio of 30:70 wt .- ^ according to Example 248 of the aforementioned US patent application.

(3) Example 91 did not contain a stabilizer. In Examples 91 and 93, that was used in stabilizer manufacture Solvent in Example 92 before mixing with the polyol blend stripped. In Example 93, the stabilizer was used without stripping off the solvent.

(4) gallons / hr

(5) Varies from about 36 to about 41 gals / hr for acrylonitrile and about 47 to about 54 gals / hr for styrene.

(6) Determined by analysis.

B is ρ ie 1 94 to 127 and P-II

In these examples, the polymer / polyols of the invention in the production of foams compared to other polymer / polyols identified by "PP" and a number. the The terms used mean:

PP-4 = A dispersion of a 55/45 acrylonitrile / styrene polymer mixed with 18 wt -.% Mischpolymerisatgehalt prepared in Polyol C using VAZO catalyst having a hydroxyl vo * n 44.3 mg KOH / g.

PP-5 = A dispersion of 78/22 acrylonitrile / styrene copolymer 29.6 wt -.% Mischpolymerisatgehalt prepared

709852/1162

in a triol of propylene oxide, ethylene oxide and glycerol i.tit with a theoretical number average molecular weight of about 5000 and a hydroxyl number of about 34. The alkylene oxide units of the triol were mainly in blocks, and the Ehdeinheit vuaren practically all ethylene oxide units _f ie the ethylene oxide was for been used to complete the triol · Based on its total weight, this triol contains about 14 wt -.% C ₂ H ₄ O.

tertiary amine catalyst = a mixture of tertiary amines blowing agent I = fluorotrichloromethane

Low density, flexible polyurethane foams have been made from the invention the above Tables XII-XIX described polymer / polyols and for comparison purposes from not obtained according to the invention Polymer / polyols produced. The in Table XX-XXl / III Foam formulations indicated were used in the amounts indicated in parts by weight.

The foam formulations were converted to polyurethane foams by the following procedure. The surfactant, the polymor / polyol and TDI were weighed into a baffle plate made of stainless steel θ-1 and 50 seconds at 2000 rpcn with 2 6-blade turbine stirrers of 6.25 cm (im Spaced 6.25 cm from each other at the base of the shaft). Stirring was stopped for 15 seconds to degas and continued for a further 5 seconds. Water and the amine catalyst mixture «Were added and mixing continued for another 5 seconds. Then stannous octoate was added and mixed for an additional 5 seconds. The foaming mixture was poured into a paper-lined 60 χ 60 χ 50 cm cardboard box and the foam

709852/1162

- 66-

ascending time determined. The foam was left overnight at room temperature allowed to cure · The physical properties of the same were measured on a 15 cm sample raised from the floor was removed from the top half of the foam pad.

The physical properties of the spaces were determined and are reported in Table XXI-XXV / 111. The following test procedures were used:
y / ercremunqszeit

Time from the formation of the complete foam formulation to the appearance of a creamy color in the same. The creaming time is proportional to the reaction speed of the formulation.
Ascent time

Time between the formation of the complete foam formulation and the maximum foam height being reached · Breathability = ASTM D-1564-69
Reflectance or color structure reflectance

Using an IDL color eye model No. Dl manufactured by Kollmorgen Corp., Attleboro, Mass., A numerical rating of 0 to 100 was made on test specimens by comparison with a series of standard specimens. A rating of "100" corresponds to a sample rated as white. Normalized ILD values

For comparison purposes, the ILD values for the actual Foam thickness were measured, converted to "normalized" ILD values of a second density by linear ratio, i.e. the normalized ILD Wprt taird calculated by multiplying of the measured ILD value with the second density and

709852/1162

Divide by the actual density.

Load ratio 3

Ratio of the ILD value at a 65 % bend to the ILD value at a 25% bend.

silicone surfactant III

Mixture of non-hydrolyzable silicone oxyalkylene

Block copolymers consisting of blocks of dimethylsiloxy units and blocks of propylene oxide and ethylene oxide units.

709852/1162

Table XX

-3 O CO OO

example

PP-2 polyols

III

IV

OH number, mg KOH / g A / S ratio of total solids; Gew.-jC Acid number; meq / g water; J

Polyolene / polyol the same or similar how

36.7

73/27

27.2

Trade product

95 96 »7 98 92-

85

15th

36.52 37
40/60 40/40
28.75 18

91

80

20th

85

15th

90

10

100

80
20th

85
15th

37.36

40/60

27.53 28.16

0.03

0.02

37.95 39.01 39.01 41.73

57

28.20 27.51 27.49

0.034 0.033 0.024 0.028
0; 034 0.014 0.033 0.03

• Example *-
59

60

61

101

80

20th
37.12

27.78 ι 0.03 £ 0.014 *

64

N) OO N) CO

Table XXI example

Formulations ι pphp Polyroer / Polyol
PP-2

Similar to Ex. 91

93

same v. Ex. 57

58 59 60 61 64

100

4.0) O.lJ 0.3

water

Amine catalyst
Stannooctoal
if current silicone agent II 1.0 TDI, 107 index 47.4

Rise time; see 91

Physical Properties

Density; lbs / ft ³ 1.49 LuEtporosity;

ftVmin / ft ^ 29.2

Rebound ability;

% "ball rebound" 29

94

100

95a

96

100

100

0.375 0.375 0.3

97

98

99

100

100

100

1Ό0

«8" Split "14

1.55 31.9 33

1.53 67.5 29 100

47.5 47.6 47.8 47.8 48.3 106 98 97 107

1.55 1.54 1.57 1.54 1.54 1.56

55.0 56.6 55.5 37.0 45.5 57.6 33 32 32 31 30

101

100

—Ft »

47.4 99

1.55 47.7 31

Table ^XXI continued

Belapiel ρ 9 ± S> 5 £ 5a 95b 9_6 92 9 ± , 99 A9J2. 101

ILD (lbs / 50 in ² )

25 % 92.5 68.5 - 72.2 71.8 80.4 80.8 85.8 87.1 81.8 84.0

65 % 191.5 137.8 - 147.0 146.8 162.8 166.0 175.3 176.8 168.0 170.5

25 % increase J % 50.5 56.4 - 48.5 49.6 52.6 52.6 51.9 51.5 51.7 52.3

Carrier factor 2.07 2.01 - 2.04 2.04 2.02 2.05 2.04 2.03 2.05 2.03 tensile strength;

lb / in * 22.4 21.0 - 16.7 16.8 20.8 20.3 20.4 20.0 20.0 20.8

Strain; % . 87 139 70 66 91 84 82 81 85 89

Tear strength;

lb / in '' 2.03 2.57 - 1.22 1.34 2.07 1.85 1.61 1.90 1.75 2.03

cn remaining M he modeling;

₀ ^

* - 75> 35.0 9.7 - 48.9 35.0 14.8 14.6 32.5 28.1 36.7 19.0

^ 90 % 53.6 19.7 - 59.4 58.2 30.5 42.8 43.7 25.4 48.6 43.0

OO N) OO

ta belle XXII

Belspl el
PP-4

Polyols:

III

A / s ratio of solids content; % OH number, Mg KOH / g

oo rise time; lake

tu density; pcf

»^ Air porosity ;, ^ ftVmin / ft ^

^ Rebound ability; fjy% "ball rebound"

** ILD (lbs / 50 in ² )

25 %

65 %

25 ^ recovery; %

Load ratio polymer / polyol; same or similar to

84
1.45

55.5
35

r.8.8
120.3
55.8
1.75

100

55/43

44.3

Commercial product

92
1.50

60.4 35

70.7 125.3 54.4 1.77

75 1.4 3

6.3 28

70.2 123.5

50.6 1.76

B. 26

40/60

35.3

85
1.50

35

103

80

20th

30/70 17.3 34.4

78
1.47

29.2 29.2

37

70.4 41.8

125.3 80.7

51.3 53.8

1.78 1.93

B.

In each case, the foam formulation contained 100 parts polymer / polyol, 4.0 parts by weight of water, 0.1 part by weight of alfine catalyst, 0.3 part by weight of stannous octoate, 1.0 Geiv.-Τέ surface-active silicone agent III and a TDI index of 110

104

80

20th

30/70 16.7 36.0

89 1.55

44.9 36

41.8 82.6 54.6 1.98

B.

105

80

20th

25/75 16.2 36.3

88 I v | 1.57 '

39.6 35

46.7 90.2 54.4 1.93

B.

• ro

v, OO

'oo ¹ * -

Table XXIII Γη ριηιΗ ^ Brunn pn

Example 1 1 over 106 107

PolymelF7Polyol ~ "

PP-2 100

PP-1 100

PP-5 -. - 100 -

same or similar to example 93 - - 100

"55 - - - - 100

Water 2.5 2.5 2.5 2.5 2.5

obfl.akt. Silicone agent I 0.5 0.5 0.2 0.5 0.5

tertiary amine catalyst 0.2 0.2 0.3 0.2 0.2

Stannous octoate 0.15 0.2 0.04 0.25 0.2

TDI, index 110 32.5 32.8 30.9 32.8 32.8

physical foam properties

Density; lb / ft ³ 2.30 2.34 2.37 2.31 2.26 hardness, 1Q-cm ILD
lb / 50 in ^e.g.

25 % bend 122 84 127 108 103

65 % bend> 250 158> 250 215 201

25 % recovery 77 57 73 68. 68

Tensile strenght; psi 27 23 28 22 27 Tear strength; lb / in 2.2 2.8 2.8 1.3 2.2

Strain; % 90 130 110 75 95 permanent deformation at 90 %

Bend; %, _o 6.5 3.4 78 7.3 5.3

Air porosity; ff ^ min / ft ^ * 8 63 9 73 41

Color eye reflectance; % 58 89 60 76 90

709852/1162

Table XXIV Formulations

example V V X 108 1.47 88 1.56 1.70 1.55 109 110 Polymer / polyol HMrte, 10 cm, ILD, Ib 50 in ² 175 PP-2 100 - - - 25 % bend 48 72 119 93 - - PP-1; - 100 - - 65 % bending 133 > 250 169 - - PP-5 ^; - - 100 - 25 % recovery 40 54 45 - - same or similar Carrier factor 21 like example 93 - - - 100 Tensile strength - - same or similar speed; psi 2.2 22nd 24 18th like example 55 - - Tear-resistant 85 100 - same or similar speed; lb / in 3.0 2.9 1.4 like example 56 - - - Strain; % 15th 140 90 65 - 100 water 4.0 4.0 4.0 4.0 permanent deformation 61 4.0 4.0 surface act. 90 % bend; % 6.5 40 33 Silicone agent I. 1.0 " 1.0 0.3 1.0 Air porosity;
ffymin / ft ^z 42 85 73 70 1.0 1.0 tert · Aminka analyzer 0.1 0.1 0.1 0.1 Color eyes 0.1 0.125 Stannous octoate 0.2 0.2 0.125 0.3 reflection; % 73 51 59 0.2 0.2 TDI, index 110 48.5 58.8 46.9 48.8 Rebound ability; 49.0 48.2 physical foam properties % "ball rebound" Rise time;, see permanent deformation; C. ^,
75 % deflection ^α 83 Density; Ib / fV 1.54 1.54 90 102.8 171 187.3 47 44.5 1.82 22nd 19th 2.0 1.8 95 70 18th _ 66 40 80 - 27 60

709852/1162

Table XXV Formulations Example l

Polymer7Polyol

same or similar to the example

Polyol H

water

ob.fl.akt. Silicone agent I.

tertiary amine catalyst

Stannous octoate TOI, index 110

Density; lb / ft ³ hardness, 10 cm ILD lb / 50 in *

25 % bend

65 % off

25 % recovery tensile strength; psi tear strength; lb / in elongation; % permanent deformation at 90 % deflection; % Air porosity; ffyniin color eye reflectance; %

112

50

50

2.5

0.5

0.2

0.225

34.8

100

2.5

0.5

0.2

0.15

36.8

113

100

4.0 1.0 0.1 0.3 48.8

114

75

25th

4.0

1.0

0.1

0.25

49.8

physical foam properties

2.17

73

138

51

18th

1.8

115

3.2

48

81

2.29 1.55

0.7

2.0

93

169

45

18th

1.4

65

33 70 59

1.46

78

146

43

17th

1.6

85

11 60 71

115

50

50

4.0

1.0

0.1

0.25

50.7

1.48

72

133

43

18th

1.7

105

7.1

59

74

100

4.0

1.0

0.1

0.225

52.7

1.52

76

103

37

14th

1.5

110

3.7

75

94

O
CD
OD

example Polymer / polyol

same or similar

such as polyol H

Blowing agent I.

water

ob.fl.akt. Silicone with I tertiary amine catalyst

Stannous octoate

TDI

index

Density; lb / ft ³ hardness, 1Q cm ILD ₉ lb / 50 in ^e.g.

25 % bend

65 % bending

25 % recovery tensile strength; psi tear strength;

I am

Strain; % permanent deformation at 90 % deflection; %

Air, porosity; tV / min / ft color eye reflectance; %

117 AA Tabel XXVt 90 119 120 1.51 121 BB 122 123 50
SO 100 Formulations 171 75
25th 50
50 66 25th
75 100 100 100 116 2.5
0.5
0.2
0.2
34.8
110 118 47 4.0
1.0
0.1
0.2
50.0
110 4.0
1.0
0.1
0.2
50.9
110 122 4.0
1.0
0.1
0.2
51.8
110 4.0
1.0
0.1
0.225
52.7
110 20th
5.0
1.3
0.1
0.225
62.4
115 15th
6.0
1.5
0.1
0.25
73.5
115 100 100 22nd * Sc haumeirenscha 39 ft Rn 2.5
0.5
0.2
0.2
32.8
110 2.21 2.5 4.0
0.5 1.0
0.2 0.1
0.15 0.2
36.8 49.0
110 110 2.0 1.52 21 1.56 1.52 0.80 0.80 69 fihysikaiischV 95 69 2.5 59 56 36 36 2.26 130 2.29 1.54 18th 132 105 112 103 64 72 103 49 48 66 40 6.5 39 37 17th IS 201 20th 95 80 21 78 18th 14th 10 11 68 2.0 39 2.6 83 2.0 1.5 1.3 1.2 27 120 11 110 100 110 70 70 2.2 3.1 0.7 7.1 4.5 3.7 30th 78 95 64 90 78 79 75 172 I.
78 5.3 91 2.0 81 86 94 80 75 41 65 90 94

OO • OO

Belgame
Polymer / polyol PP-2

PP-5

same or similar

as in Example 55 water

ob.fl.akt. Silicone agent I.
ter amine catalyst stannous octoate TDI, index 110

Density; lb / ft ³

Hardness, 10 cm ILD lb / 50 in ^

25 % bend

65 % bending

normalized ILD values, 2.30 pcf / 1.50 pcf and 30.1 f. solids

25 % bend

65 % bend> 250

Tabel XXWII DD 124 EE FF 125 Formulations 100 100 100 - ££ 2.5 100
2.5 4.0 4.0 100
4.0 100 0.2 0.5 1.0 1.0 1.0 2.5 0.3
0.04
30.9 0.2 0.1
0.2 0.2
32.8 48.5 0.1
0.125
46.9 0.1
0.2
49.0 0.5 physical viewing properties 0.2
0.15
32.5

2.30 2.37 2.26 1.47 1.70 1.54

122
> 250

127
> 250

103 201

88 175

119

90 171

125
> 250

111 217

90 179

106

91 173

709852/1162

Table XXVIII

example GG HH 126 II 127 Polymer7Polyol Art PP-4 PP-I same or PP-I same or similar to uiie similar to ufie Example 91 Ex. 91 lot 100 100 100 100 100 water 5.0 5.0 5.0 6.0 6.0 Amine catalyst 0.13 0.10 0.10 0.10 0.10 if.fl.act.siliconwith tel I 1.0 1.0 1.0 1.0 1.0 Stannous octoate 0.25 0.25 0.25 0.20 0.20 TDI index 105 105 105 105 105 Creaming Time; sec - 11 11 11 11 Rise time; sec 132 74 77 85 87 Density; pcf - 1.20 1.22 1.07 1.11 Breathability; SCFH - 1.0 1.7 3.3 3.5 Reflectance center; % * 63 69 77 57 74

* The reflectance values were measured on a hand-mixed foam with a block size of etuia 55 χ 55 χ 60 cm · For the measurements were made using cross sections of the block center.

709852/1162

Claims (1)

Claims .1> - polymer / polyol preparation that is produced by reacting with a polyisocyanate is convertible into a polyurethane product, the polymer / polyol at the temperature for converting the preparation in the polyurethane product is normally liquid and the polymer of the polymer / polyol is in situ in the polyol of one or more polymerizable, ethylenically unsaturated, chemically bound Halogen virtually free monomers is formed, characterized in that it is a stable dispersion of small particles of the polymer in a polyol of relatively low numerical value represents average molecular weight by the monomer or the monomer mixture in situ in the absence polymerized by any alkyl mercaptan in a polyol blend comprised of about 55-93% by weight of a polyol having a numbered polymerized weight average molecular weight not above about AOOO and about 45-5 w / l of a polyol having a number average molecular weight not below about 5000. 2, - preparation according to claim 1, characterized in that the Polyol mixture about 70-90 wt .- ^ polyol with a number average molecular weight not exceeding about 4000 and about 10-30 wt .- ^ polyol with a number average Molecular weight included not below about 5000. 3 · - preparation according to claim 1, characterized in that the Polyol mixture about 70-95 wt .- ^ polyol with a number average molecular weight not above about 4000 and about 5-30 wt .- ^ polyol with a number average Molecular weight included not below about 5000. 7 0 9 8 5 2/1162 4 · preparation according to claim 1, characterized in that the
Polyol mixture etuia 80-90 Gew .- ^ " ¹ OIyöl with a number average molecular weight not over etu / a 4000 and
etu / a 10-20 wt .- $ polyol having a number average molecular weight not less than etu / a 5000. 5.- preparation according to claim 1 to 4, characterized in that the amount of polymer dispersed in the polyol mixture is about 4-40
Gew.-jS, preferably about 15-35 wt .- ^, based on the weight of the preparation, is 6, - preparation according to claim 1 to 5, characterized in that that the polymer comprises polymerized acrylonitrile. 7, - preparation according to claim 6, characterized in that the Polymer also contains polymerized styrene. B.- preparation according to claim 6 and 7, characterized in that the weight ratio of polymerize) acrylonitrile to polymerized Styrene iia polymer between 20:80 to 100: 0, preferably between 25:75 and 100: 0. 9, - preparation according to claim 6 and 7, characterized in that the weight ratio of polymerized acrylonitrile to polymerized Styrene in the polymer is between about 40:60 to 85:15, preferably between about 60:40 to 85:15. 10. Preparation according to claims 6 to 9, characterized in that the polymer still contains polymerized methyl methacrylate. 11.- preparation according to claim 10, characterized in that the weight ratio of polymerized acrylonitrile to polymerized Methyl methacrylate in polymerize styrene about 25:25:50 amounts to. 709852/1162 12, - preparation according to claim 1 to 11, characterized in that, that is the number average molecular weight of the polyol low molecular weight in the range of about 400-4000 and that of the higher molecular weight polyol between about 5000-20,000. 13 · - preparation according to claims 1 to 11, characterized in that the number average molecular weight of the lower molecular weight polyol being about 1000-4000 and that of the higher molecular weight polyol is between about 5000-15. 14, - A method for the preparation of the polymer / polyol preparation according to claim 1, characterized in that the monomer or monomers in the presence of a free radical catalyst in the absence of any alkyl mercaptan in a polyol mixture of about 55-95 wt -.% Of a polyol with a numerical average molecular weight not exceeding about 4000 and about 45-5 weight - not polymerized% of a polyol having a number average molecular weight below about 5000, to form a stable dispersion of small particles of the polymer in the polyol is obtained.. 15, - A method according to claim 14, characterized in that a polyol is used, about 70-95 Geiu. jS-polyol having a number average molecular weight not exceeding about 4,000 and about 5-30 wt -.% Of polyol having a number average Molecular weight included not below about 5000. 16.- The method according to claim 14 and 15, characterized in that that as a catalyst 2,2'-azo-bis-isobutyronitrile or a free one Free radical peroxy ester catalyst is used. 709852/1162 17, - Process for the production of optionally foamed Polyurethanes, characterized in that one is known per se Way a mixture of (a) a polymer / polyol preparation according to claim 1 and (b) an organic polyisocyanate in the presence of (c) a catalyst for the reaction of (a) and (b) sou / ie optionally (d) a blowing agent and (e) a foam stabilizer implements. 18, - The method according to claim 17, characterized in that daG for Production of flexible foams Reaction and foaming take place according to the one-shot process, the polymer / polyol preparation Contains alkylene oxide adduct of a polyhydroxylalkane, the blowing agent Is water and this is used in such an amount that a foam with a density below 0.028 g / ccm receives. The patent anu / old: 709852/1