JPS5939446B2 - Polymer/polyol composition, method for producing the same, and method for producing polyurethane products from the composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polymer/polyol compositions that react with polyisocyanates to form polyurethanes.

Polymer/polyol dispersions have been used previously and are still used today in the production of polyurethane products.

Such dispersions yield polyurethane products that exhibit a variety of desirable properties. There is a wealth of literature on the preparation of polymer/polyol dispersions, including, for example, Stamberger U.S. Pat. No. 3,304,273, U.S. Pat. Patent No. 338
Scharf et al. and Curyla (1cury1a) Canadian Patent No. 735
No. 010 and No. 785835: Pizzi
U.S. Patent No. 3,823,201 for R.
amlOw) et al., U.S. Patent Application No. 431,080 (19
(filed on January 7, 1974): U.S. Patent No. 395 by Ramlo 1st Class
No. 3,393 and DeWald, US Pat. No. 3,655,553.

Each of these prior art techniques, including the Sternberger patent, involves in-situ polymerization of one or more ethylenically unsaturated monomers in a polyol to form a dispersion of small polymer particles dispersed within the polyol. 1 shows the preparation of a polymer/polyol dispersion.

This dispersion is then mixed and reacted with polyisocyanates and other polyurethane-forming agents to form polyurethanes, thus serving as a readily efficient and economical means of improving polyurethane properties. This method and the resulting polymer/polyol dispersions continue to be widely accepted and used in the polyurethane industry. Thus, while conventional polymer/polyol dispersions have found wide application throughout the polyurethane industry, there has been an increase in the development of complex, high-speed, large-format equipment for handling, mixing, and reacting the polyurethane-forming ingredients. Therefore, a need has arisen to improve polymer/polyol dispersions.

That is, there has been a need for more stable dispersions so that the dispersions can be stored until use without exhibiting significant sedimentation. In the past, there was little concern in industrial practice about the seediness, viscosity or flowability of polymers/polyols. However, the current state of the polyurethane manufacturing industry has advanced to the point where the above considerations are of great importance. Since the mechanical systems used for mass production are now very complex, there is a great deal of interest in flowability, seeding, and viscosity. In addition, conventional methods cannot produce dispersions of relatively low molecular weight polyols such as dipropylene glycol in a stable state, and therefore low molecular weight substances are used as polyol components in polymer/polyol dispersions. It had become less desirable than high molecular weight substances. Low molecular weight polyols are useful where low viscosity is essential and are useful in foams, paints and coatings, and some sealants. The present invention provides highly stable and highly permeable polymer/polyol compositions with low or virtually no seeding.

The present invention also allows relatively high polymer contents in the dispersion at lower viscosities and without compromising stability. These and other benefits are obtained by using small amounts of high molecular weight polyols in low molecular weight polyols. The use of polyol blends to produce polymers/polyols is disclosed in the Sternberger, Sharpe et al., Curaira, Pitzuni, Lamoureaux et al., and Dewald patents and Lamoureaux et al. patent applications mentioned above. Also,
The Sternburger British patent describes the use of low molecular weight polyols in polymer/polyol dispersions. However, none of the above-mentioned documents discloses or even suggests the benefits of the present invention by adding a small amount of a high molecular weight polyol to a low molecular weight polyol as described herein. The Dewald patent discloses that the polyol is preferably a triol, but may contain diols or tetrols having the same molecular weight range in amounts as high as 40%.

Thus, the molecular weight of these polyols does not exceed 5,500, preferably less than 5,000, and advantageously 150
It is in the range of 0 to 5,000, preferably 3,000 to 5,000. The Pitzuni patent discloses the use of polyol blends consisting of two polyols of the same molecular weight.

The Lamoureaux et al. patent application teaches the preparation of polymer/polyol dispersions from polyol blends and vinyl halide or vinylidene monomers and claims improvements in stability. Also,
The patent application states that stable graft copolymer dispersions derived from vinyl monomers can be used as chain transfer aids if the monomer is vinyl chloride, vinyl bromide, vinylidene chloride or vinylidene bromide. It is stated that it has been found that it can be produced at temperatures below 100° C. in the absence of oxidation. So, a polymer/polyol made from a halogenated monomer! It is unacceptable for the production of such polyurethanes due to the formation of acidic decomposition products which can interfere with the production of ζ polyurethanes and often poison the catalyst. The Lamoureaux et al. patent discloses the production of polymers by polymerizing vinyl monomers in the presence of a chain transfer agent alkyl mercaptan in a specially formulated unsaturation-containing polyol having a specified amount of apparent critical unsaturation.
Disclosed is the production of polyol dispersions.

Such polymer/polyol dispersions have very limited application in the polyurethane field because the polyurethane products made therefrom are malodorous. This malodour arises from the fact that the patent requires the chain transfer agent alkyl mercaptan when making the polymer/polyol dispersions, so such dispersions are used particularly in products such as pinerests or armrests, safety pads, etc. It has become unacceptable to consumers. Additionally, the use of alkyl mercaptans, as required by this patent, poses major problems due to the highly unpleasant and strong odor of mercaptans and the negative impact on workers who manufacture and use the dispersions. are doing. Thus, stable polymers/polyols with the advantageous properties of the compositions of the present invention are made from ethylenically unsaturated monomers by using a blend of large amounts of low molecular weight polyols and small amounts of high molecular weight polyols. is not disclosed, taught, or even suggested in any of the above-mentioned documents or in any of the known prior art methods.

In general, the present invention provides polymer/polyol compositions with high stability and filtration properties.

In addition to these properties, the composition is highly flowable and virtually free of scrap and seed crystals. The polymer particles of the compositions of the present invention are small in size, in preferred embodiments less than 30 microns in diameter. Polymer/polyol compositions can be made with unusually low viscosities when according to the present invention. It can also be manufactured with relatively high polymer content. The polymer/polyol compositions of the present invention can be easily converted into polyurethane products exhibiting special properties. In some cases, the special properties include high load bearing capacity and high color fastness. The deficiencies of the conventional method mentioned above are:
According to the present invention, the low molecular weight base polyol desired to be used in the preparation of the polymer/polyol composition can be beaten by adding a small amount of a high molecular weight polyol.

The subsequent production of polyurethane does not require the use of potentially harmful halogenated monomers. Furthermore, there is no need to use unpleasant malodorous substances such as alkyl mercaptans. In its broadest aspects, the present invention provides polymer/polyol compositions convertible to polyurethanes by reaction with polyisocyanates, which are normally liquid at the temperature at which the compositions are converted to polyurethanes; 1. The composition is formed from one or more polymerizable ethylenically unsaturated monomers with virtually no chemically bonding halogens in situ in the polyol without the presence of any alkyl mercaptans. The above benefits are achieved by obtaining stable liquid polymer/polyol compositions.

The polymer/polyol composition of the invention preferably has a
It is liquid at ℃. The present invention provides a polyol blend comprising from about 55 to about 95 weight percent of a polyol having a number average molecular weight of no higher than about 4,000 and from about 45 to about 5 weight percent of a polyol having a number average molecular weight of no lower than about 5,000. Stable small particle polymer/polyol dispersions are provided by in situ polymerization of the monomer or monomer mixture. Another benefit of the present invention is that a wider range of free radical catalysts can be used in the polymerization without critical narrow limitations and without compromising stability or permeability. For example, azo or peroxide catalysts can be used if desired or required;
Catalysts that are safer and easier to use can be selected. The polymer/polyol compositions of this invention can be converted into high modulus polyurethane elastomers and foams by reaction with polyisocyanates.

The invention will now be described with respect to specific embodiments.

The polymer/polyol compositions of the present invention contain from about 55 to about 95% by weight of one or more polyols (hereinafter also referred to as low molecular weight polyols or LMW polyols) having a number average molecular weight not higher than 4000, preferably about 70% by weight. ~90% by weight and one or more polyols (hereinafter also referred to as high molecular weight polyols or HMW polyols) having a number average molecular weight of not less than about 5000 from about 5 to 45%, preferably from about 10 to about 30% by weight A stable liquid dispersion of a polymer in a polyol blend consisting of %.

However, the above weight % is based on the low molecular weight (LMW) in the composition.
) Based on the total amount (weight) of polyol and high molecular weight (HMW) polyol. However, in terms of molecular weight, there is in fact no lower limit to the molecular weight of the LMW polyol and no upper limit to that of the HMW polyol, as long as both polyols are liquid and the blend and final polymer/polyol have the desired viscosity. The molecular weight of the LMW polyol is as low as, for example, the molecular weight of dipropylene glycol, preferably in the range of about 400 to about 4,000, most preferably in the range of about 1,000 to about 4,000. The molecular weight of the HMW polyol is preferably about 5,000 to about 20,000.
and most preferably about 6,000 to about 15,000. The respective molecular weight is a critical parameter, comparable to the respective equivalent weight, e.g. in obtaining the benefits of the present invention.
No difference has been found between diols and triols as HMW or LMW polyols when their molecular weights are truly equal. In this specification,
The number average molecular weight of the polyol is used. This is a theoretical (or apparent) value calculated from the theoretical functionality and hydroxyl number. The true number average molecular weight starts from the true functionality (
(or theory) It can be said that it is slightly lower depending on how far below the functionality value is. Obviously, to ensure a stable dispersion,
The LMW polyol and HMW polyol should be compatible with each other. The proportion of polymer in the polymer/polyol compositions of the invention ranges, for example, from about 4 to about 40% by weight, preferably from about 15 to about 35% by weight, based on the total weight of the polymer/polyol composition. .

Virtually all of the polyols previously used in the art to make polymers/polyols can be used in the HMW of the present invention, so long as they meet the number average molecular weight and compatibility requirements set forth above.
and can be used as LMW polyol. Examples of polyols useful in making polymer/polyol compositions according to the present invention are polyhydroxyalkanes, polyoxyalkylene polyols, and the like.

Among the polyols that can be used, one or more of the following groups known to polyurethane manufacturers are selected:
Mention may be made of polyols, singly or in mixtures: (a) alkylene oxide adducts of polyhydroxyalkanes: (b)
) alkylene oxide adducts of non-reducing sugars and sugar derivatives; (c) alkylene oxide adducts of phosphoric acid and polyphosphoric acids; (d) alkylene oxide adducts of polyphenols; (e) from natural oils such as castor oil etc. Polyol.

Examples of alkylene oxide adducts of polyhydroxyalkanes include, inter alia: ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1. 41,5- and 1,6-dihydroxyhexane, 1,2-, 1,3-, 1,4- 1,6-
and 1,8-dihydroxyoctane, 1,10-dihydroxydecane, glycerin, 1,2,4 trihydroxybutane, 1,2,6-trihydroxyhexane, 1,
Alkylene oxide adducts such as 1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol, caprolactone, polycaprolactone, xyrite, arabite, solpit, mannite, etc. A preferred class of alkylene oxide adducts of polyhydroxyalkanes are ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, adducts of trihydroxyalkanes. Other polyols that may be used are alkylene oxide adducts of non-reducing sugars in which the alkylene oxide has 2 to 4 carbon atoms.

Among the non-reducing sugars and sugar derivatives that are contemplated are sucrose, alkyl glucosides such as methyl glucoside, ethyl glucoside, etc., ethylene glycol glucoside, propylene glycol glycoside, glycerin glucoside, 1,2,
These include glycol glycosides such as 6-hexanetriol glucoside, as well as alkylene oxide adducts of alkyl glycosides as described in U.S. Pat. No. 3,073,788. Still other useful polyols are polyhydric phenols, preferably their alkylene oxide adducts, where the alkylene oxide has 2 to 4 carbon atoms.

Among the polyhydric phenols that are contemplated, the following are found, for example: bisphenols A1 bisphenols F1 condensates of phenols with formaldehyde, novolac resins: condensates of various phenolic compounds with acrolein,
The simplest of this kind is 1,1,3-tris(hydroxyphenyl)propane: condensates of various phenolic compounds with glyoxal, glutaraldehyde and other dialdehydes;
- 1,2,2-tetrakis(hydroxyphenol)ethane: and analogs. Other useful polyols are phosphoric acid and alkylene oxide adducts of polyphosphoric acid. Preferred alkylene oxides include ethylene oxide, 1,2-epoxypropane, epoxybutane, 3-chloro-1,2-epoxypropane, and the like. Preferred for use in this connection are polyphosphoric acids such as phosphoric acid, phosphorous acid, tripolyphosphoric acid, polymetaphosphoric acid, and the like. The polyols used can have hydroxyl values that vary over a wide range.

Generally, the hydroxyl number of the polyol used in the present invention can range from about 20 or less to about 850 or more. Hydroxyl number is polyol 17
It is defined as the η number of potassium hydroxide required to completely hydrolyze the fully acetylated derivative prepared from The hydroxyl number can also be defined by the following equation: where the hydroxyl number of the OH-polyol, f=functionality, ie the average number of hydroxyl groups per polyol molecule, M. w. - Molecular weight of the polyol.

The exact polyol used will depend on the end use of the polyurethane product to be made.

The molecular weight of the hydroxyl number is suitably selected to provide a flexible to semi-rigid foam or elastomer when the polymer/polyol made from the polyol is converted to polyurethane. The polyol preferably has a hydroxyl number of from about 50 to about 150 for semi-rigid foams and from about 30 to about 70 for flexible foams. Such ranges are not intended to limit the invention and are merely illustrative of the many possible combinations of the polyol co-reactants described above. The most preferred polyols for use in the present invention include poly(oxypropylene) glycols, triols and higher functionality polyols.

These polyols also include poly(oxypropylene-oxyethylene) polyols. However, desirably the oxyethylene content should constitute up to 80% of the total, preferably up to 60%. When ethylene oxide is used, it can be incorporated in any manner along the polymer chain. In other words, ethylene oxide can be incorporated into internal blocks or as end blocks, or randomly distributed along the polymer chain. As is well known in the art, the most preferred polyols herein contain varying amounts of unsaturation. As taught by Sternberger, unsaturation inherently has no adverse effect on the formation of polymers/polyols according to the present invention unless the type is effective or the type is high to result in a crosslinked polymer. It does not affect the aspect either. In the polymerizable ethylenically unsaturated monomer that can be used in the present invention,
・Includes those without rogens.

Monomers of this type include polymerizable ethylenically unsaturated hydrocarbon monomers and molecules with carbon, hydrogen and 0, S or N
A polymerizable ethylenically unsaturated organic monomer consisting of at least one of these is included. Monomers useful in the method of the invention include:
It is a polymerizable monomer characterized by having at least one C-C polymerizable ethylenically unsaturated group present in the molecule.
Monomers can be homopolymers/polyols or copolymers/
They can be used singly or in combination to produce reactive compositions of polyols. These monomers are well known in the art and include: butadiene, isoprene 1,4-pentadiene 1,6
~Hexadiene, 1,7-octadiene, styrene, α
- Hydrocarbon monomers such as methylstyrene, methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, etc., cyanostyrene, nitrostyrene, N-N - substituted styrene lyacrylic acid, methacrylic acid, methyl acrylate, such as dimethylaminostyrene, acetoxystyrene, methyl 4-vinylbenzoate, phenoxystyrene, p-vinyldiphenyl sulfide, p-vinylphenyl oxide, etc.
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isopropyl methacrylate, octyl methacrylate, methacrylonitrile, alpha-ethoxyethoxyacrylate, alpha-acetaminoacrylic Methyl acid, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate, N-N-dimethylacrylamide, N-N-dibenzylacrylamide, N-butylacrylamide,
Acrylic acid and substituted acrylic acid monomers such as methaqualformamide; vinyl acetate, vinyl alcohol, vinyl butyrate, isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl methoxy acetate, vinyl benzoate, vinyl toluene, vinyl naphthalene, vinyl methyl ether, vinyl ethyl ether,
Vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-
Dihythro 1, 2-pyran, 2-butoxy-2! -vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, vinyl ethyl sulfide, vinyl ethyl sulfone, N-methyl-N-vinylacetamide, N-vinylpyrrolidone , vinyl esters, vinyl ethers, vinyl ketones, etc., such as vinyl imidazole, divinyl sulfide, divinyl sulfoxide, divinyl sulfone, sodium vinyl sulfonate, methyl vinyl sulfonate, N-vinyl pyrrole, etc.; dimethyl fumarate, dimethyl maleate, maleic acid, croton. acid, fumaric acid, itaconic acid, monomethyl itaconate,
t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl allyl alcohol acrylate, glycol monoester of itaconic acid, vinylpyridine, etc.

Any known polymerizable monomer can be used,
The compounds mentioned above are examples of monomers suitable for use in the present invention, and are not intended to be limiting. Any known chain transfer agent, except alkyl mercaptans, can be present if desired. The preferred monomers used to make the polymers of the polymer/polyol compositions of the present invention are acrylonitrile alone as a homopolymer and a mixture of acrylonitrile and styrene as a copolymer. The relative weight ratio of acrylonitrile to styrene is, for example, from about 20:80 to
About 100:0 preferably ranges from about 25:75 to 100:0, more preferably when using a low molecular weight polyol, such as about 200 or less, the weight ratio is about 60:4
It should be between 0 and about 85:15. Copolymers of acrylonitrile, methyl methacrylate and styrene have also been used. Catalysts useful in preparing the polymer/polyol compositions of the present invention include free-radical vinyl polymerization catalysts such as peroxides, persulfates, perborates, percarbonates, and azo compounds, or those previously described. Any other suitable catalyst may be identified in patents and patent applications. To name a few, such catalysts include 2,21-azobisisobutyronitrile, dibenzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, diisopropyl peroxide carbonate, t-butyl peroxy-2-ethylhexanoate. , t-butylperpivalate, 2.5
-dimethylhexane-2,5-jeper-2-ethylhexoate, t-butylperneodecanoate, t-butyl perbenzoate, t-butyl percrotonate,
These include t-butyl perisobutyrate and di-t-butyl perphthalate. Azobis(isobutyronitrile) is a preferred catalyst. This is because it does not exhibit any unpleasant odors or require special handling in the plant due to potential hazards.The concentration of the catalyst is not critical and can be controlled within a wide range. It can change.

As a typical range, the concentration may vary from about 0.1 to about 5.0% by weight, based on the total feed to the reactants. An increase in catalyst concentration up to a certain point increases monomer conversion, but further increases do not increase the conversion rate effectively. On the other hand, product stability increases with increasing catalyst concentration. Improved. The selected catalyst concentration is usually the optimum value considering all factors including cost. Polymerization can also be carried out with an inert organic solvent present that does not dissolve the polymer.

Illustrative examples include toluene, benzene, and the like, which are known in the art as suitable solvents for the polymerization of vinyl monomers. The only requirement in selecting the solvent and polyol is that they do not interfere with the polymerization reaction of the monomers.

When an inert organic solvent is used, it is generally removed from the reaction mixture by conventional means prior to the preparation of the polyurethane foam using the polymer/polyol. The temperature range is non-critical, from about 8'C or less to about 150C or less.
Although it may vary over a range from 105°C to 135°C, the preferred range is 105°C to 135°C.

The catalyst and temperature should be selected such that the catalyst has an adequate rate of decomposition with respect to the dwell time in the reactor in the case of a continuous flow reactor or with respect to the feed time in the case of a semi-batch reactor. The preferred method used in making the polymer/polyol compositions of the present invention is to polymerize the monomers in the polyol while maintaining a low monomer/polyol ratio throughout the reaction mixture during this polymerization. It includes things.

This results in a polymer/polyol composition in which, in preferred cases, essentially all of the polymer particles have a diameter of 30 microns or less, generally 1 micron or less. Such low ratios are achieved by using process conditions that rapidly convert monomer to polymer. In practice, low monomer/polyol ratios can be achieved by controlling the temperature and mixing conditions in semi-batch and continuous operations, and also by gradually adding monomer to the polyol in semi-batch operations. It is maintained by This method can be carried out in various embodiments, such as semi-batch reaction, continuous back-mixing and agitation tank reactor, etc. In the latter case, a second stage can be used to incrementally increase monomer conversion. The mixing conditions used are those that are achieved using a back-mixing reactor (eg a stirred flask or stirred autoclave). Such reactors keep the reaction mixture relatively homogeneous and thus, in some tubular reactors (
For example, in the first stage of a "MareO" reactor, localized high monomer levels, such as occur when such reactors are conventionally operated with all monomer added to the first stage. /polyol ratio is prevented. When using a semi-batch process, the feed time (as well as the ratio of starting polyol in the reactor to polyol fed with monomer) can be varied to vary the product viscosity.

Generally, longer feed times will result in higher product viscosity, and for a given polyol and polymer content, the use of a slightly wider acrylonitrile/styrene range may be acceptable. Crude polymer/polyol compositions typically contain small amounts of unreacted monomer.

Such residual monomer can be converted to additional polymer by using a 1/2 step operation.

In this operation, the product of the first stage (backmixing reactor) is
It is passed through a second stage, for example a conventionally operated Marco reactor or a tank reactor without a stirrer. Preferred temperatures used in preparing polymer/polyol compositions in accordance with the present invention are any temperature at which the half-life of the catalyst is no more than about 25% of the residence time in the reactor.

For example, the half-life of the catalyst for a given reaction time is 6 minutes or less (preferably 1.5-2 minutes or less). The half-life of a catalyst decreases with increasing temperature. For example, azobisisobutyronitrile has a half-life of 6 minutes at 100°C. The maximum temperature used is not very critical, but should be below the temperature at which significant decomposition of the reactants or products occurs. In the process used to make the polymer/polyol of the present invention, monomers are polymerized in a polyol.

Usually the monomer is soluble in the polyol. By first dissolving the monomer in a small portion of the polyol and adding the resulting solution to the miscellaneous portion of the polyol at the reaction temperature, mixing of the monomer and polyol is facilitated and the contamination or blockage of the reactor is avoided. It was found that this can be reduced or eliminated. If the monomer is not soluble in the polyol, it can be dispersed in the polyol prior to polymerization using known methods, such as dissolving the insoluble monomer in another solvent. . The conversion of monomers to polymer achieved by this method is extremely high. (For example, generally at least 75% to 95% conversion of monomer is obtained). When copolymerizing acrylonitrile and styrene, the acrylonitrile to styrene ratio in the polymer is always slightly lower than the acrylonitrile to styrene monomer ratio in the feed.

This is because styrene tends to react slightly more rapidly than acrylonitrile. For example, if the monomers anonocrylonitrile and styrene are fed in a weight ratio of 80:20, the resulting polymer will have a weight ratio of acrylonitrile to styrene of about 79:21 or 78:22.

The present invention is a highly stable polymer/polyol composition characterized by relatively high polymer content, small polymer particle size without scrap or seeding, and convertibility into very useful polyurethane elastomers and foams. will be provided.

More particularly, the present invention provides, with certain polyols, increased styrene to acrylonitrile ratio or polymer content, yet provides a product with improved stability. Also, more stable polymers/polyols can be produced with lower molecular weight polyols than can be achieved by conventional methods. The polymer/polyol compositions of the present invention are stable dispersions such that all the polymer particles remain suspended without any significant settling even after standing for several months. The polymers/polyols of the present invention consist of a dispersion of relatively small particle sizes in which the polymer particles, which are either individual particles or agglomerates of individual particles, are comprised in a preferred embodiment of essentially all Particles are smaller than 30 microns.

Thus, in a preferred reformation, all of the essential mass (i.e., about 99% or more) of the product passes through the seven filters used in the Sawagen test described in connection with the "Example" below. This ensures that polymer/polyol products can be successfully processed in the full range of relatively complex machinery systems currently used in the mass production of polyurethanes, which include, for example, the production of relatively large particles. Included are those using impingement-type mixing that require the use of filters that cannot tolerate any significant amounts. Less stringent applications are satisfied when about 50% of the product passes through the filter. , some applications may find useful products with only about 20% passing through the filter.Thus, the polymers/polyols of the present invention have at least 20% passing through the filter, preferably at least 50% passing through the filter. Preferably, all of the substance passes through the filter.What has been discovered in this invention are polymer/polyol dispersions with higher than standard polymer content in glycols or other very low molecular weight polyols. Moreover, it has industrially acceptable properties of low scrap, low permeable solids content, and non-sedimentation tendency.

A polymer/polyol is a normally stable insoluble polymer (eg, acrylonitrile polymer or acrylonitrile/styrene copolymer or any other monomer system) dispersion in a base polyol. It is also known that the molecular weight of the base polyol appears to have a significant influence on the dispersion stability of the polymer/polyol. in general,
The higher the molecular weight of the base polyol, the better the dispersion stability. Therefore, the production of stable polymers/polyols in low molecular weight polyols has heretofore been difficult. According to the present invention, the low molecular weight polyol has a high molecular weight (500
Improved dispersion stability is obtained by adding small amounts (5-45%) of polyols (0 or more). The effectiveness of a high molecular weight polyol in improving the dispersion stability of a polymer/polyol depends on (1) its molecular weight and (2) its concentration in the polyol plaid.

The higher the molecular weight, the greater the improvement in dispersion stability achieved with the same amount of addition. Similarly, the higher the amount of high molecular weight polyol used, the greater the improvement in dispersion stability achieved. Significant improvements in dispersion stability are achieved by adding high molecular weight polyols in small amounts, on the order of 5-45% by weight. However, other factors must also be taken into account when selecting the amount and type of high molecular weight polyol, such as the effect on foaming properties and foam properties. The polymer concentration of the polymer/polyol compositions of the present invention can be adjusted by adding additional polyol to provide the appropriate polymer concentration for the desired end use.

In this way, polymer/polyol compositions can be made with a polymer concentration of, for example, 20%, and the polymer concentration can be reduced to as low as 4% by adding additional polyol, or alternatively, , the composition can be prepared directly by the method of the invention at a polymer concentration of 4%. The present invention also provides new polyurethane products made with the new polymer/polyol compositions and new methods of making such products.

The novel polyurethane product comprises a polymer/polyol composition of the invention (a), an organic polyisocyanate (b), a catalyst (c) for reacting these (a) and (b) to form a polyurethane product, and When the foam is to be produced, it is produced by reacting a blowing agent and a foam stabilizer. This reaction and foaming operation is
It can be carried out in any suitable manner, preferably by a one-shot method, although a prepolymer one-shot method can be used if desired. Organic polyisocyanates useful in making polyurethane products according to the present invention are organic compounds containing at least two isocyanate groups. Such compounds are well known in the art. Suitable organic polyisocyanates include hydrocarbon diisocyanates, such as alkylene diisocyanates and arylene diisocyanates, as well as the known triisocyanates. As examples of suitable polyisocyanates, the following may be mentioned: 1,2-diisocyanatoethane, 1,3-diisocyanatopropane, 1,2-diisocyanatopropane, 1,4-diisocyanato. butane,
1,5-diisocyanatopentane, 1,6-diisocyanatohexane, bis(3-isocyanatopropyl) ether, bis(3-isocyanatopropyl) sulfide,
1,7-diisocyanatoheptane, 1,5-diisocyanato-2,2-dimethylpentane, 1,6-diisocyanato-3-methoxane, 1,8-diisocyanato-octane, 1,5-diisocyanato-2,2・4-trimethylpentane, 1,9-diisocyanatononane, 1,10-diisocyanatopropyl ether of 1,4-butylene glycol, 1,11-diisocyanatoundencane, 1
・12-diisocyanatododecanebis(isocyanatohexyl) sulfide, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotrilene, 1,3-diisocyanato-0- Xylene 1,3-diisocyanato-m-xylene, 1,3-
Diisocyanato-p-xylene 2,4-diisocyanato-1-chlorobenzene, 2,4-diisocyanato-1
-Nitrobenzene 2.5-diisocyanato-1-nitrobenzene 4,4'-diphenylmethylene diisocyanate, 3,3'-diphenylmethylene diisocyanate and the formula: [wherein X is 1.1 to 5 (preferably 2.0
-3.0)] and mixtures thereof.

Catalysts useful in making polyurethanes according to the present invention include the following: : (a) Bis(dimethylaminoethyl)ether, trimethylamine triethylamine, N-methylmorpholine, N-ethylmorpholine,
N-N-dimethylbenzylamine, N-N-dimethylethanolamine, N-N-N! -tetramethyl-1・3
Butanediamine, triethylanolamine, 1,4-
Tertiary amines such as diazabicyclo[2.2.2]octanepyridine oxide, etc.; (b) Tertiary phosphines, such as trialkylphosphine, dialkylbenzylphosphine, etc.; (c) alkali metal and alkaline earth metal Strong bases such as hydroxides, alkoxides and phenoxides; (d) Acidic metal salts of strong acids such as ferric chloride, stannic chloride, stannous chloride, antimony trichloride, bismuth nitrate, bismuth chloride, etc.: (e) acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetyl-acetonimine,
Bis-acetylacetone alkylene diimine, salicylaldehyde imine, etc., and BelMg, . Zn. ．． Cd,
．． Pb,. Ti,. Zr,. Sn,. AslBi. Cr
．． M.O. Mn. Fe. C.O. Various metals such as Ni or M
Chelates of various metals, such as those obtainable from ions such as OO2++, UO2+, etc.: (f) Ti(0
R)4, Sn(0R)4, Sn(0R)2, Al(0R
) 3 (wherein R is alkyl or aryl) and phenolades of various metals, and the well-known chelates of titanium obtained by the above-mentioned method or an equivalent method; β
Reaction products with diketones and 2-(N-N-dialkylamino)alkanols; (g) e.g. sodium acetate, potassium laurate, potassium hexanoate, stannous acetate, stannous octoate, stannous oleate , lead octoate, manganese naphthenate, and metal desiccants such as cobalt; and alkali metals, alkaline earth metals, Al, Sn. Pb, Mn, . CO,. N
i and salts with various metals such as Cu: (h) tetravalent tin;
Trivalent and pentavalent As. Organometallic derivatives of Sb and Bi and metal carbonyls of iron and cobalt.

Among the organotin compounds worth mentioning are the dialkyltin salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin monobis(4 -methylaminobenzoate), dibutyltin-bis(6-methylaminocaproate), and the like.

It is likewise possible to use trialkyltin hydroxides, dialkyltin oxides, dialkyltin dialkoxides or dialkyltin dichlorides. Examples of these compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin bis(isopropoxide), dibutyltin bis(
2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and the like. Tertiary amines can be used as primary catalysts to promote reactive hydrogen/isocyanate reactions or as secondary catalysts in combination with one or more of the metal catalysts described above.

A metal catalyst or a mixture of metal catalysts can also be used as a promoter without the concomitant use of an amine. The catalyst may be present in small amounts, for example about 0.001% based on the weight of the reaction mixture.
Used in amounts of ~5%. When the product to be produced is a polyurethane foam, this may require a small amount of a polyurethane blowing agent, such as water, in the reaction mixture (e.g., from about 0.5 to about 50% based on the total weight of the polymer/polyol composition).
% water), or by the use of a blowing agent which is vaporized by the exotherm of the reaction, or by a combination of these two methods.

Examples of polyurethane blowing agents include trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dichloromethane, trichloromethane 1.
Included are 1-dichloro-1-fluoroethane, 1,1,2-trichloro-1,2,2-trifluoromethane, hexafluorocyclobutane, octafluorocyclobutane, and the like. Other types of blowing agents include N-NI-dimethyl-N-
Included are thermolabile compounds that release gas on heating, such as NL dinitroliterephthalamide and the like. A generally preferred method for producing flexible foams is to use water or a combination of water and a fluorocarbon blowing agent such as trichloromonofluoromethane. The amount of blowing agent used will vary depending on factors such as the desired density of the foam product. Also included are small amounts of foam stabilizers, such as from about 0.001% to 5.0% by weight, based on the total reaction mixture, such as U.S. Pat.
It is also within the scope of this invention to use "hydrolyzable" polysiloxane-polyoxyalkylene block copolymers, such as those described in US Pat.

Other useful foam stabilizers include U.S. Pat. No. 3,505,377
"non-hydrolyzable" polysiloxane-polyoxyalkylene block copolymers, such as those described in US Pat. No. 888,067 (December 24, 1969) and British Patent No. This type of copolymer is characterized by the fact that the polysiloxane moiety is bonded directly to the polyoxyalkylene moiety by a carbon-to-silicon bond rather than by a carbon-to-oxygen-to-silicon bond. Different from polyoxyalkylene block copolymers.These various polysiloxane-polyoxyalkylene block copolymers preferably have 5 to
Contains 50% by weight polysiloxane polymer with the balance being polyoxyalkylene polymer. Polyurethanes produced according to the invention can be used advantageously in a variety of applications.

For example, the present invention allows for the production of polyurethane foams. Such foams may be desirably used in the slab foam market. Additionally, the polymers/polyols of the present invention can be used to form polyurethane elastomers where relatively low molecular weight polyols must be used to provide the required stiffness. The polymers/polyols according to the invention can also be used to form polyurethane products for applications requiring high load-bearing properties. Polyurethanes made in accordance with the present invention are also useful in applications where conventional polyurethanes are used, such as armrests, safety pads, mattresses and automobile bumpers.
The various symbols used in "Example" below and elsewhere in this specification have the following meanings: "A/MMA/S" represents the weight ratio of acrylonitrile to methyl methacrylate to styrene.

"A/S" or "A:S" refers to the weight ratio of acrylonitrile to styrene. "Cps" stands for sensepoise.

"Part" represents part by weight.

"PolyA" represents polyacrylonitrile.

"PolyS" represents polystyrene. "Ppm" represents parts by weight per million parts by weight.

"Psig" stands for 1b/In2 gauge pressure. Temperatures are in °C unless otherwise specified. "Pli" represents 1b/line 1n.

"Residue" represents unreacted monomer.

"Rpm" indicates the number of revolutions per minute.

"TD" is a mixture of 80% 2,4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate.

[VAZO-64] or "VAZO" represents 2.i-azobisisobutyronitrile.

"TMSN" is tetramethylsuccinonitrile (a decomposition product of Bazo-64 above). "Ratio" is based on weight.

"%" represents a percentage by weight unless otherwise specified.

[TBPO" represents t-butyl per-2-ethylhexoate.

The numbered examples illustrate the invention.

The alphanumeric examples are comparative examples and do not exemplify the present invention. Polyols with an alpha alphabet are low molecular weight polyols, and polyols with a number are high molecular weight polyols.

"LMW" stands for low molecular weight.

"HMW" stands for high molecular weight.

Polyol ratios are based on a weight basis, where the percentage of low molecular weight polyol is given first and then the percentage of high molecular weight polyol is given.

The calculated hydroxyl number shown in the table of examples below is based on the total polymer content that can be calculated and the hydroxyl number of the base polymer.

Light transmission data was obtained by using 500 mμ wavelength light and the polymer/polyol was diluted to 0.01% with a clear solvent.

Polyol I propylene oxide, ethylene oxide and sorbitol glycerin blend (weight ratio 80/2
0) having a theoretical number average molecular weight of about 10,800 and a hydroxyl number of about 28.

Alkylene oxide units are present primarily in the blocks, and the terminal units are virtually all ethylene oxide units.
That is, ethylene oxide is used to "cap" the polyol. The polyol contains about 8% by weight ethylene oxide units, based on the total polyol weight. A polyol made from propylene oxide and glycerin, about A polypropylene oxide triol having a theoretical number average molecular weight of 6000 and a hydroxyl number of about 28.7.

A polypropylene oxide-polyethylene oxide triol having a theoretical number average molecular weight of about 6000 and a hydroxyl number of about 26.1, made from polyol propylene oxide, ethylene oxide and glycerin.

Alkylene oxide units are present primarily in the blocks, and the terminal units are virtually all ethylene oxide units. That is, ethylene oxide converts the triol into
It is used to "cap". The triol contains approximately 14% by weight C2H4O based on its total weight. Polyol A tripropylene glycol.

Polyol B Dipropylene glycol.

Polyol C-F These polyols have the following corresponding theoretical number average molecular weights and hydroxyl numbers, respectively, for polypropylene oxide diols made from propylene oxide and dipropylene glycol; Polyol G made from propylene oxide and glycerin.

A polypropylene oxide triol having a theoretical number average molecular weight of about 3000 and a hydroxyl number of about 55.4. Polyol H A polypropylene oxide-polyethylene oxide triol made from propylene oxide, ethylene oxide and glycerin and having a theoretical number average molecular weight of about 3000 and a hydroxyl number of 56.4.

Virtually all of the ethylene oxide units are located internally within the molecule. That is, virtually none of them constitutes a terminal unit. Based on its total weight, the polyol contains approximately 8
Contains % by weight C2H4O. Polyol J A polypropylene oxide polyethylene oxide triol made from propylene oxide, ethylene oxide and glycerin and having a theoretical number average molecular weight of about 3600 and a hydroxyl number of about 46.7.

All of the ethylene oxide units are internally located. That is, virtually none of them constitutes a terminal unit. The polyol contains about 14% by weight C2H4O based on its total weight.

Polyol K Made from propylene oxide, ethylene oxide and glycerin.

A polypropylene oxide-polyethylene oxide triol having a theoretical number average molecular weight of about 2700 and a hydroxyl number of about 62.14. All of the ethylene oxide units are internally located, and the polyol is
It contains about 8% by weight C2H4O based on its total weight. Polyol L A polypropylene oxide-polyethylene oxide triol having a theoretical number average molecular weight of about 3400 and a hydroxyl number of about 49, made from propylene oxide, ethylene oxide and glycerin.

All of the ethylene oxide units are internally arranged as a continuous floc, and the polyol contains 10% by weight C2H4O, based on its total weight. Preferred compositions of the present invention are essentially free of polymer particles greater than 30 microns in diameter.

If in the following test 99% by weight or more of the composition
A composition meets the above criteria if it successfully passes a 0 mesh sieve and a 700 mesh sieve. That is, a 470y sample of the composition to be tested is diluted with 940f of anhydrous isopropanol to reduce viscosity effects. The diluted sample was passed through a 2.41n2 150 mesh sieve and then
．． Pass through a 41n2 700 mesh sieve. (These sieves should be cleaned, dried and weighed before testing). The sieves are then washed with isopropanol to remove any polyol, dried and weighed. The difference between the final sieve weight and the initial sieve weight corresponds to the amount of polymer that did not pass through the sieve. A 150 mesh sieve has a square mesh with an average opening of 105 microns, so it is a "Standard Tyler" 150 square mesh sieve.

The 700 mesh sieve is manufactured from Dutch twill weave with an average opening of 30 microns and is manufactured by Ronningen Peter Company, Kalamazu, Michigan.
ingen-PeterCompany) Newsletter 462
67-R explains ★A.

The centrifugable solids polymer/polyol composition was centrifuged at about 3000 rpm, 1
Centrifuge at 470 G radial centrifugal force for about 24 hours.

The centrifuge tube is then inverted and allowed to drain for 4 hours. The non-flowing cake remaining at the bottom of the tube is recorded as a weight percent of the initial weight of the test composition. Tippin
g) Place the previous transparent layer polymer/polyol composition in a small test tube and centrifuge for about 24 hours, then observe the liquid in the test tube and measure the height of the transparent layer above the top. and,
This height is expressed as % liquid height in the test tube. Examples 1-37 and Examples A-F In a continuously stirred tank reactor equipped with a baffle plate and an impeller driven at approximately 800 rpm, Examples 1-3
37 and Examples AF were carried out sequentially.

Prior to entering the reactor, the feed components were passed through an in-line mixer to ensure complete mixing before the feed components were continuously pumped into the reactor. The internal temperature of the reactor was controlled to within 1°C by applying controlled heating or cooling to the outside of the vessel. The product exited the reactor through a back pressure regulator. [This regulator was adjusted to provide a 101b/In2 gauge backpressure in the reactor]. The product was then discharged to a product receiver via a water-cooled tubular heat exchanger. For testing, portions of the crude product were vacuum stripped at 2 mm pressure and 120-130°C. The conversion rate was determined by gas chromatographic analysis of the amount of unreacted monomer present in the crude product before stripping. Experimental conditions and experimental results for Examples 1-37 and A-F are listed in Tables 1-- below.

80/20 of 1,4-bucundiol and polyol I
(Weight) To the mixture were added acrylonitrile and styrene in a weight ratio of 78/28 together with bazo.

In the feed, the concentration of Bazo was 0.5% by weight, and the content of monomer + Bazo was 20.07% by weight. Further, the feed rate of the polyol mixture was 2270/111-, and that of monomer + bazo was 5707/Hr. The product is 28367/
The J quality balance was 99.86%.
However, the product formed a layer overnight, illustrating the effect of compatibility between polyols. Examples 27-30 In these examples, a polyol blend of 85% by weight Polyol K and 15% by weight Polyol was used.

In each case the reaction temperature was 125° C. and the residence time was 12 minutes. Otherwise, the conditions and methods shown in Table v below and the general procedures described in the previous examples were used. Examples 38-48 These examples compared the polymers/polyols made in Examples 17 and 24-29 to other polymers/polyols.

Other polymers/polyols are “PP” which can be explained below.
and numbers. Thus, in this example, the following designations are used: Acrylonitrile-styrene (50/50) copolymer prepared in polyol J using PP-1 Bazo catalyst with a hydroxyl number of 36.9 ηKOH/7 A dispersion with a copolymer content of 18%.

PP-2 72% acrylonitrile and 28% styrene copolymerized in polyol L using a Bazo catalyst, hydroxyl number is 36.7m9K0H/7, viscosity at 25°C is 2854c
Copolymer content 27.2-2% dispersion with ps.

78% copolymerized in polyol H using PP-3 TBP0
32.9% copolymer content of acrylonitrile and 22% styrene with hydroxyl number between 37.5 and KOH/7
Dispersion.

Amine catalyst bis(2-dimethylaminoethyl)ether 70% by weight
and 30% by weight of dipropylene glycol.

TDI 2,4-tolylene diisocyanate 80% by weight and 2,6
- a mixture with 20% by weight of tolylene diisocyanate.

Silicone surfactant 1 Silicone surfactant 55% by weight and C4H9O(C2H4O)18(C3H6O)13.7
H (90% by weight) and C9Hl9C6H4OCC2H
4O] 10.5H (10% by weight) mixture with 45% by weight of the mixture.

Test Methods The following test methods were used in the examples shown in the table below: Low-density flexible polyurethane foams were prepared from polymers and polyols prepared independently.

In this case, the foam formulations shown in Table, Table X and Table M were used. The amounts given in the table are parts by weight. The foam formulation was converted to polyurethane foam using the following method.

i.e. surfactant, polymer/polyol and T
The DI was weighed into an 81 mm stainless steel beaker with a baffle plate, and this was stirred using two 2.51 n 6-blade turbine stirrers (separated 2.51 n apart at the base of the shaft).
Mixed at 2000 rpm for seconds. Stirring was stopped for 15 seconds to degas, and stirring was continued again for 5 seconds. Add the water and amine catalyst mixture and continue mixing for an additional 5 seconds. The stannous octoate was then added and mixed for 5 seconds. The foaming mixture was poured into a paper-lined 245' x 247 x 20" box and the bubble rise time was recorded. The foam was allowed to cure overnight at room temperature. For a 61n sample taken from the bottom of the soil half of the foam bun. The physical properties of the foam were measured.The following physical properties of the foam were determined and are shown in Table, Table X and Table M.

As the data in Table It can be used to

Also, flexible foams made with polymers/polyols having lower acrylonitrile to styrene ratios exhibit higher load carrying capacity and are relatively non-tarnishing, as shown in the table and the data in the table. The initial assumption was that adding 15% of the high molecular weight polyol in the foam formulation would reduce the load characteristics of the foam by perhaps 10%. However, the foam evaluation data shown in Tables 1 and 2 showed that the load-bearing properties of the foam were not impaired in any way, which was unexpected. Examples 49-93 and Examples L-0 Examples 49-93 and Examples L-0 were carried out continuously in a continuously stirred tank reactor equipped with a baffle plate and an impeller driven at approximately 800 rpm.

Prior to entering the reactor, the feed components are passed through an in-line mixer to ensure complete mixing before the feed components are continuously pumped into the reactor. The internal temperature of the reactor is regulated to within 1° C. by applying controlled heating or controlled cooling to the outside of the vessel. The product exits the reactor through a back pressure regulator. [This regulator adjusts to provide a 101b/In2 gauge backpressure in the reactor. ] The product is then discharged to a product receiver via a water-cooled tubular heat exchanger. For testing, portions of the crude product are vacuum stripped at 2 mT1L pressure and 120-130°C. Conversion is determined by gas chromatographic analysis of the amount of unreacted monomer present in the crude product before stripping. Experimental conditions and experimental results for these examples are listed in Tables X below.

Although most of the details of the polyols used have already been given, new polyols used in some examples are described below. Polyol A polypropylene oxide-polyethylene oxide polyol having a theoretical number average molecular weight of about 12,000 and a hydroxyl number of about 27.87, made from propylene oxide, ethylene oxide and Solpit.

Alkylene oxide units are primarily present in the block, and the red end units are virtually all ethylene oxide units. In other words, ethylene oxide
It is used to capture This polyol contains about 8.6% by weight of ethylene oxide units, based on its total weight. Polyol V made from 65% by weight propylene oxide and 35% by weight ethylene oxide and Solpit, about 103
A polyol having a theoretical number average molecular weight of 0.00 and a hydroxyl number of approximately j★27.77.

Alkylene oxide units are present primarily in the blocks, and the terminal units are virtually all ethylene oxide units. That is, 15% by weight of ethylene oxide is used to "cap" the triol. This polyol contains about 44% by weight ethylene oxide, based on its total weight. Examples 94-127 and Example P
In these examples, polymers/polyols made in accordance with the present invention were compared with the preparation of foams with other polymers/polyols designated as "PP" and by numbers such as those mentioned above and below. .

In these examples, the following new designations were used: PP
- 18 wt% copolymer content dispersion of acrylonitrile-styrene (55/45) copolymer prepared in polyol G with a 4-bazo catalyst and having a hydroxyl number of 44.3 w KOH/y.

PP-5 Acrylonitrile loose styrene (78/22) copolymer prepared in a triol prepared from propylene oxide, ethylene oxide and glycerin with a theoretical number average molecular weight of about 5000 and a hydroxyl number of about 34 Copolymer content 29 .6% by weight dispersion.

The alkylene oxide units of the triol are present primarily in the floc, and the terminal units are virtually all ethylene oxide units. That is, ethylene oxide is used to "cap" the triol. This triol contains about 14% C2 based on its total weight.
Contains H4O. t-Amine-catalyzed mixture of tertiary amines.

Blowing Agent 1 Fluorotrichloromethane From polymers/polyols produced according to the present invention as described in Tables to Table X shown above and, for comparison, from polymers/polyols produced without relying on the present invention. , a low density flexible polyurethane foam was prepared.

At that time, Table XX to Table XXVI! The foam formulation shown in I was used. The amounts shown in these tables are parts by weight. The foam formulation was converted to polyurethane foam using the following method.

i.e. surfactants, polymers/polyols and TD
I was weighed and placed in a stainless steel beaker with a baffle plate of 81, and this was placed in a 2.51N six-blade turbine stirrer 2.
(placed 2.51n apart at the base of the shaft) for 60 seconds at 2000 rpm. Stirring was stopped for 15 seconds to degas, and stirring was continued again for 5 seconds. Add the water and amine catalyst mixture and continue mixing for an additional 5 seconds. The stannous octoate was then added and mixing continued for 5 seconds. The foaming mixture was poured into a paper-lined 24' x 24' x 2σ box and the bubble rise time was recorded. The foam was allowed to cure overnight at room temperature. The foam properties were measured on a 61n sample taken from the bottom of the upper half of the foam bun. The foam physical properties that can be measured are shown in Tables XM to XXVII.

The following new tests were also conducted: Cream time The time from the formation of a full foam formulation to the appearance of a cream color in the formulation.

Cream time is proportional to the reaction rate of the formulation. Elevation Time Time from formation of a complete foam formulation to reaching the maximum height of the foam.

Breathability (Breathabjllty) ASTM D-1564-690 Reflectance or Color Eye (COlOr-Eye) Reflectance Co., Ltd.
OllmOrgenCOrp) 1DL colora [■■
A rating on a scale of 100 was made by comparison with a series of standards.

A rating of "100" corresponds to a test piece that is rated as white. For normalized 1LD value comparisons, ILD values measured at the actual density of the foam are converted by linear proportionality to "normalized" LD values at a second density.

That is, this standardized 1LD value is calculated by multiplying the measured ILD value by the second density and dividing by the actual density. Load ratio 65% deflection ILD value to 25% deflection ILD value ratio.

A mixture of a non-hydrolyzable silicone-oxyalkylene block copolymer comprising a block of silicone surfactant dimethylsiloxy units and a block of propylene 5-oxide units and ethylene oxide units.

Claims (1)

Claims: 1. A polymer/polyol composition convertible into a polyurethane product by reaction with a polyisocyanate, which is normally liquid at the temperature at which the composition is converted to said polyurethane, and which contains said polymer/polyol. In polymer/polyol compositions in which the polymer is formed from one or more polymerizable ethylenically unsaturated monomers that are substantially free of chemically bonded halogen in situ in the polyol, said polymer has a relatively low polyol having a number average molecular weight provided as a stable dispersion in small to medium particles, the stable dispersion of the polymer having a number average molecular weight of from about 55 to about 95% by weight and not less than about 5000; prepared by in-situ polymerization of the monomer or monomer mixture without the presence of any alkyl mercaptan in a polyol blend comprising from about 45 to about 5% by weight of a polyol having an average molecular weight; and A polymer/polyol composition comprising the polymer dispersed in the blend. 2. The polyol blend comprises from about 70 to about 90% by weight of a polyol having a number average molecular weight of no greater than about 4,000 and from about 10 to about 30% by weight of a polyol having a number average molecular weight of no less than about 5,000. Compositions as described in Section. 3. The polyol blend comprises from about 70 to about 95 weight percent of a polyol having a number average molecular weight of no greater than about 4,000 and from about 5 to about 30 weight percent of a polyol having a number average molecular weight of no less than about 5,000. Compositions as described in Section. 4. The polyol blend comprises from about 80 to about 90 weight percent of a polyol having a number average molecular weight of no greater than about 4,000 and from about 10 to about 20 weight percent of a polyol having a number average molecular weight of no less than about 5,000. Compositions as described in Section. 5. The composition of claim 1, wherein the amount of polymer dispersed in the polyol blend is from about 4 to about 40% by weight, based on the weight of the composition. 6. The composition of claim 1, wherein the amount of polymer dispersed in the polymer blend is from about 15% to about 35% by weight, based on the weight of the composition. 7. The composition according to claim 6, wherein the polymer is polymerized acrylonitrile. 8. The composition of claim 7, wherein the polymer further contains polymerized styrene. 9. The composition of claim 8, wherein the weight ratio of polymerized acrylonitrile to polymerized styrene is in the range of 20:80 to 100:0. 10. The composition of claim 9, wherein the weight ratio of polymerized acrylonitrile to polymerized styrene in the polymer ranges from 25:75 to 100:0. 11. The composition of claim 9, wherein the weight ratio of polymerized acrylonitrile to polymerized styrene in the polymer ranges from about 40:60 to 85:15. 12. The composition of claim 9, wherein the weight ratio of polymerized acrylonitrile to polymerized styrene in the polymer ranges from about 60:40 to 85:15. 13. The composition of claim 7, wherein the polymer further contains polymerized methyl methacrylate. 14 The weight ratio of polymerized acrylonitrile to polymerized methyl methacrylate to polymerized styrene is about 25 to about 25 to about 5.
14. The composition according to claim 13, which has a molecular weight of 0. 15 The number average molecular weight of the polyol having the lower molecular weight is within the range of about 400 to about 4000, and that of the polyol having the higher molecular weight is within the range of about 5000 to about 200.
The composition according to claim 1, which is within the range of 0.00. 16 The number average molecular weight of the polyol having the lower molecular weight is within the range of about 1000 to about 4000, and that of the polyol having the higher molecular weight is within the range of about 5000 to about 15
The composition according to claim 1, wherein the composition is within the range of 0.000.