DE2538116A1 - LIQUID POLYMER / POLYOL PREPARATIONS - Google Patents

Description

Polymer. /Polyol.- preparations used in the manufacture of polyurethane foams are suitable are known. These preparations can be made by polymers of one or more olefinically unsaturated, in monomers dissolved or dispersed in a polyol in an aniuesunity free radical catalyst can be produced. These polymer / polyol preparations have the valuable properties that the polyurethane foams made from them have higher load-bearing properties Properties as by unmodified polyols as well as those from them to give manufactured, solid polyurethane elastomers a higher modulus than unmodified polyols.

The polymer / polyol preparations that have hitherto been used are essentially preparations made from polyols and acrylonitrile or acrylonitrile-styrene mixtures. The preparations usually contain about 80% Geuu-70 polyol and about 20% by weight of polymer. The polymer is an acrylonitrile homopolymer or a copolymer of about 40-55 % acrylonitrile and 60-45%

609813/0914

₂ _ 2538118.

- $ styrene. Part of the polymer is due to the polyol to form a graft copolymer that the remaining Polymer particles stabilized so that they remain dispersed in the polyol. The higher load-bearing properties and the higher modulus of the polyurethanes produced from these polymer / polyol preparations is ascribed to the polymer in the preparations.

Attempts at the large-scale production of polymer / polycl-pre-

Polyurethanes prepared with more than 20 % by weight of polymers, which / thus give even higher load-bearing properties and nodules, have encountered various difficulties. Thus, when the polymer in the preparation consists of acrylonitrile alone and the polymer content is significantly above 20 Geiu .- ^ o, the preparations usually have undesirably high viscosities, and large grains usually form. These grains cause difficulties in the manufacture, handling and processing of the preparations (for example, the grains can be used in the reactors in which the preparations are made, as well as the filters in the feed lines of the relatively complex machines in which polyurethane foams are currently made from

clog)

Preparations are produced /. If the polymer is in the preparation consists of acrylonitrile and styrene in the above-mentioned relative amounts and the polymer content is significantly above 20 wt .- / o, Excessively large, large grains are also formed.

The difficulties in producing polymer / polyol preparations, in which the polymer is made from acrylonitrile and styrene are particularly severe in the process of trials of Example 6 of Canadian Patent 785,835 in which

609813/0914

such monomers can be used. In the latter process, very unsatisfactory preparations are produced due to the formation of grains manufactured. A substantial improvement in the particle size of such polymer / Palyol preparations is achieved by using the method described in US Pat Bilgischen patent specification 708 115 achieved process described. However, even this method still leaves room for further improvement with regard to the formation of granules at polymer contents significantly above 20 wt.

The previously known polymer / polyol preparations have been made from polyols with molecular weights of about 3000 and more. The use of low molecular weight polyols results in polymer / polyol preparations which can be converted into polyurethanes with properties which can only be advantageously obtained if low molecular weight polyol parts are present in the polyurethane structure. However, the use of low molecular weight polyols has not proven to be completely satisfactory because the polymer / polyol preparations obtained are not stable to phase separation, and this is according to current industry standards, in particular with polymer contents of 15 Ge \ u + -% and more, would be desirable.

The viscosity of a polymer / polyol preparation is related to ease of handling, e.g., pumping, of the preparation and the ability of the polyurethane containing the preparation to form Mixtures for filling the molds are very important. It is desirable to keep the viscosity to a minimum for a given polymer content to maintain the ease of handling of the preparation for a given value of the improvement in load-bearing properties of the polyurethane and module (i.e. with an opposing polymer

609813/0914 -

content) and the deformation of such polyurethane to facilitate forming mixtures.

In addition to the commercially available polymer / polyol preparations described above many other polymer / polyol preparations are also known; see. e.g. US PSS 3 3G4 273, 3 383 351 and 3 823 201, the Canadian PS 735 010 and the German PSS 1 152 536 and 1 152 537.

It is therefore an object of the present invention to provide improved Polymer / polyol preparations as well as the creation of easily processable polymer / polyol preparations with over 20% by weight of an acrylonitrile-styrene polymer, those for the production of polyurethane foams with relatively high load-bearing properties and firm Polyurethanes with a relatively high modulus can be used. The invention also provides stable polymer / polyol preparations created that contain relatively low molecular weight polyols. In addition, the polymer / polyol preparations according to the invention have with an opposite polymer content and polyol molecular weight, relatively low viscosities.

The present invention relates to new liquid from the polymer / polyol preparation consisting essentially of:. (1) 45-90 wt -% of a polyoxypropylene polyol having a molecular weight of at least 1500 and (2) 55-10 Ge \ u.- % of an acrylonitrile-styrene Polymersates consisting essentially of (a) 60-90 wt .- ^ o polymerized acrylonitrile and (b) 40-10 wt -.% polymerized styrene, the polymer is present in the form of particles which are stably dispersed in the polyol and the preparation continues to be practical

603813/0 914

2538118

is free of polymer particles with a diameter of more than 30 fticron and the preparation is made by polymerizing a monomeric mixture of acrylonitrile and styrene in the polyol. The new polymers / polyols can be converted into new polyurethane foams with high load-bearing properties and into solid polyurethane elastomers with high moduli. The present invention does not encompass five particular polymer / polyol preparations falling under the above definition but which have already been described together with many other polymer / polyol preparations; nor does it include the polyurethanes made from these five preparations. The five excluded preparations are (A) the preparation of example HID of US Pat. No. 3,823,201, which is composed of 80% by weight of a polyol with a molecular weight of about 4800 and 20% by weight of a polymer in the form of the polymer consists of a mixture of 66% acrylonitrile and 33 % styrene; (B) the preparation of Example Uli of US Pat. No. 3,823,201, which is composed of 80% by weight of a polyol derived from a polyoxypropylenetriol with a molecular weight of 3000 and maleic anhydride, and 20% by weight of a polymer in the form of the polymer consists of a mixture of 68% by weight of acrylonitrile and 32 % by weight of styrene; (Jc), the preparation of Example 4V of the Belgian Patent 788 115, consisting of 80 Gem -.% of a polyol having a molecular weight of about 3000 and 20 wt, -one polymers in the form of the polymer from a mixture of 70 wt -.% of acrylonitrile and 30 gem. % styrene; (D) the preparation uon example 1 of GB PS 1,321,679, which is made from 60 % by weight of a polyol with a molecular weight of about 4,000

809813 / 09U

2538118

/.- by addition of 87 parts of propylene oxide and 13 Geu Geiu.-Teilsn ethylene oxide with propylene glycol, and 40 Geui. ~ / £ of a polymer in the form of the polymer from a mixture of 80 Geuj. ~ ^c / o by weight of acrylonitrile and 20 ^ Is made of styrene; and (E) the preparation of Example 4 of GB'PS 1 321 679, which is made from 70 Ge \ u .-% of a polyol with a Rolekulargeiuicht of etu / a 4000, prepared by the addition of 87 parts propylene oxide and 13 Gem Parts of ethylene oxide on propylene glycol, and 30 % by weight of a polymer in the form of the polymer from a mixture of 80% of acrylonitrile and 20 % of styrene. In general, the polymer / polyol preparations according to the invention have lower viscosities than polymer / polyol preparations with the same polymer content and polyol starting material and lower or high ratios of acrylonitrile to styrene. The viscosities of the new preparations are usually between 500-15000 centipoises at 25 C.

Figure 1 is a graph of weight percentage of polymer / polyol preparations passing through a 700 mesh sieve against the weight ratio of acrylonitrile to styrene in the for Manufacture of the preparations used acrylonitrile-styrene mixtures, u / when the polyol ("Polyol I" described below) Has a molecular weight of 5000.

Fig. 2 is the graphic representation of the percentage of weight on centrifugable solids in polymer / polyol preparations against the acrylonitrile: styrene weight ratio in the production of the preparations used acrylonitrile-styrene mixtures, uienn that Polyol ("Polyol I" as defined below) is a molecular weight of 5000 has.

609 8 1 3 / 09U

2538118

Fig. 3 is the curve of the viscosity (in centipoises at 25 ° C.) of the polymer / polyol preparations against the acrylonitrile: StyrDl weight ratio of the acrylonitrile-styrene mixtures used to produce the preparations, if the polyol ("Polyol 1" according to the following Definition) has a molecular weight of 5000 »

Figure 4 is the weight percentage graph for manufacture Acrylonitrile-styrene used by polymer / polyol preparations » Healing against the acrylonitrile: styrene weight ratio in the Mixtures if the polyols ("Polycl I" and "Polyol III" according to the following definition) have molecular weights of 5000. The weight percentage the mixture is based on the sum of the dishes the blends and polyols used to make the preparations.

Fig. 5 is the graph of the percentage by weight of the polymer / polyol preparations; which pass through a 700 mesh sieve against the acrylonitrile: styrene weight ratio of the preparation used Acrylonitrile-styrene mixtures used when the polyol ("polyol II "according to the following definition) has a molecular weight of 3000.

6 is the graph of the percentage by weight of centrifugable solids in polymer / polyol preparations versus the acrylonitrile: styrene weight ratio in the acrylonitrile-styrene mixtures used to make the preparations when the polyol ( "Polyol II" as defined below ) has a molecular weight of 3000.

609813/0914

Fig. 7 is the curve of the viscosities (in centipoises at 25 ° C.) of the polymer / polyol preparations against the acrylonitrile * styrene weight ratio the acrylonitrile used to manufacture the preparations Styrene mixtures, if the polyol ("Polyol II" according to following definition) has a molecular weight of 3000.

Fig. 8 is the curve of the weight percentage of the acrylonitrile-styrene mixtures used in the production of polymer / polyol preparations goguri inter alia acrylonitrile: styrene weight ratio in the mixtures when the polyols ("Polyol II" and "Polyol Uli" according to the following Definition) Have molecular weights of 3000. The business

weight percentage of the mixes is based on the sum of the weights the mixtures used to manufacture the preparations

and polyols.

Figure 9 is the weight percentage graph for manufacture Acrylonitrile-styrene mixture used by polymer / polyol preparations against the acrylonitrile: styrene weight ratio in the mixtures if the polyol ("Polyol UI" according to the following definition) has a molecular weight of 3000. The weight percentage The mixture is based on the sum of the weights of the used to manufacture of the preparations used and the polyol.

Fig. 10 is the graph of the percentage by weight of the preparation Acrylonitrile-styrene mixtures used by polymer / polyol preparations versus the molecular weights of the polyols, ujenn the polyol molecular weight is between 1500-6000. The weight percent

The set of weights of the mixture is based on the sum / amount used to make the

Preparations used mixtures and polyols.

609813 / 09U

2538118

Fig. 11 is the weight percentage graph for manufacture Acrylonitrile-styrene mixtures used by polymer / polyol preparations versus the molecular weights of the polyols, if the polyol molecular weight between 4500-6GQQ. The weight percentage The mixture is based on the sum of the weights of the used to manufacture of the preparations used mixtures and polyols.

For the preparation of the preparations according to the invention with the above Particle size must take into account the mutual relationships of the variables of the preparations. So the width depends the usable polymer content (which corresponds approximately to the percentage by weight of the monomeric mixture used) on the molecular weight and the chemical composition of the polyol and the weight ratio of acrylonitrile to styrene in the monomer f-mixture from (which is approximately the ratio of polymerized acrylonitrile corresponds to polymerized styrene). A greater latitude with regard to the polymer content is achieved with higher molecular weight polyols and polyols obtained containing some ethylene oxide, and to / ar inside the structure or at the end of the polyol molecule as end groups. Ethylenoxidendgruppen are opposite internal Ethylene oxide groups, particularly in the case of low molecular weight polyols, are preferred. Next depends on the width of the usable Acrylonitrile: styrene ratio for a polyol with a given Molecular weight depends on the higher the polymer content. Usually, the higher the polymer content, the narrower the useful one. Range from acrylonitrile to styrene. The functionality of the polyol does not appear to be an important variable in relation to the polymer particle size to be. As an example, the following mutual

6098 13/0914

25381 IS

Relationships for polyols with molecular weights of 5000, 3000 or *. 2000 *

A. for a triol with glycerol as the starting material, which consists of 86 wt .- $ Cxypropylene groups and 14 wt .- $ oxyethylene groups and has a molecular weight of about 5000, the usable acrylonitrile: styrene weight ratio is between about 90:10 and 60 : 40 with a polymer content not exceeding about 25% by volume , with a preferred monomer range from 85:15 to 70:30. For 25-30 Gem.-yS polymer, the available acrylonitrile: styrene range with such a triol is between 90:10 and 70:30, preferably 85:15 to 75:25. With an acrylonitrile: styrene weight ratio of 80:20, a polymer / polyol with up to 45 % or more polymer can be produced with this triol.

B. For a triol with glycerol as the starting material consisting of oxypropylene groups and a fiolekulargewicht of about 3000, the acrylonitrile can. Geu styrene / layer ratio of between about 90:10 and 60:40 for a polymer content up to about 20 Gem - %, preferably from 85:15 to 70:30. With an acrylonitrile: styrene weight ratio of 80:20, a suitable product with up to 25-30 % by weight of polymer is obtained using a diol based on dipropylene glycol which contains oxypropylene groups and has a molecular weight of about 3000.

C. For a diol originating from dipropylene glycol with jxypropylene groups and having a molecular weight of about 2000, the acrylonitrile: styrene weight ratio can be between about 90:10 and 70:30 for a polymer content of up to about 20% by weight , preferably 85:15 to 75i25, vary. For an acrylonitrile: styrene - \ / ratio "

B098 13 / 09U

won'80: 20 you can use a polymer .. polyol with up to about 25 wt .- ^ Polymer can be produced using such a DidI.s.

In the present application, unless otherwise stated, the polyol molecular weights number average molecular weights, calculated using the following equation (Α), based on the functionality of the to produce the Polyols used starter compound and that determined experimentally Hydroxyl number of the polyol.

The polyols used in this invention include both Propylenoxidhomopolymerisate as well as copolymers with at least 55 wt .- o polymerized propylene oxide / and up to 45 wt -.% Of another polymerized alkylene oxide such as ethylene oxide or butylene oxide. The polyol preferably contains 80-99 wt -.% Polymerized propylene oxide and 20-1 wt -.% Of polymerized ethylene oxide. the

he
Polyols can be made from residues of a rod compound, such as ethylene glycol, dipropylene glycol, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-trihydroxybutane, 1,1 O-dihydroxydecane, glycerine, 1,2,4-trihydroxybutane, 1, 1,1-trimethylolpropane, hexanetriol, etc. contain. The polyols have molecular weights of at least 1500, preferably at least 2000, for example from 2000-6000. Regarding the particle size of the polymer in a polymer / polyol preparation made from a polyol, the molecular weight of the polyol is the more important parameter compared to the squivalent weight (e.g. there is no difference between a diol and a triol if the molecular weights are the same.)

609813 / 09U

The for the production of the polymer / polyol preparations according to the invention Polyols used can have a hydroxyl number that is above a wide range uariated. Usually the hydroxyl numbers are Polyols used according to the invention between etuia 20 and less up to about 150 and more. The hydroxyl number is defined as the number of mg Kaliuiiihydroxid, which for the complete hydrolysis of the completely acetylated derivative, made from 1 g. Polyol, are necessary. The hydroxyl number can also be expressed by the following equation To be defined.

_{0H =} 5 ^ J _- JM

Molgeuj.

Thereby means
OH = hydroxyl number of the polyol

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

MolgGiu. = number average molecular weight of the polyol

For the production of a special preparation according to the invention Polyol used depends on the end use of the polyurethane product to be manufactured, in that the hydroxyl number is chosen so that that flexible or semi-flexible foams or elastomers are obtained, when the polymer / polyol made from the polyol in a polyurethane is converted. The polyols preferably have a hydroxyl number of about 50-150 for semi-flexible foams and from around 20-70 for pliable foams. Mixtures of polyols can also be used.

When l / learn about the production of the inventive polymer / Polyol preparations, the monomers in the polyol are polymerized,

609813 / 09U

2538118

wherein a low ratio of fionomer to polyol is maintained in the reaction mixture during the polymerization. These low ratios are achieved by using process conditions that result in rapid conversion of the βοπο-merone to polymer. In practice, a low ratio of Fionomerem to polyol in the semi-batch and continuous processes by controlling the temperature and mixing conditions and in the semi-batch process also durcn slow addition of the monomers maintained to the polyol, which may be any temperature are applied, wherein the half-life of the catalytic converter is no longer than 6 minutes. The mixing conditions used are achieved by using a backmixing reactor (eg a stirred flask or stirred autoclave). These reactors keep the reaction mixture relatively homogeneous and thus prevent localized high ratios of fionomer to polyol, as occur in certain tubular reactors, for example in the first stages of "Marco ^II reactors, because these occur in the usual way with the addition of all of the monomers can be operated in the first stage, but tubular reactors, for example Marco reactors, can be used if these are modified in such a way that the monomers are added batchwise at different stages.

When using a semi-discontinuous process, the loading times can (as well as the polyol content in the reactor at the beginning against the polyol charge with the conomers) in order to achieve Changes in product viscosity can be varied. Longer loading times usually lead to high product viscosities and can use etu; as broader acrylonitrile: styrene

■ 609-81-3 / 0914

Allow range for a given polyol and polymer content. The exposure times are not very important, especially with continuous process.

The crude polymer / polyol preparations usually contain minor amounts Amounts of unreacted monomers. These residual monomers can be converted into additional by using a two-step process Polymer can be converted.

For the production of the polymer / polyol preparations according to the invention, any temperature can be used at which the half-time of the catalyst is not more than 6 minutes, preferably not more than 1 ^ 5-2 minutes. The half-life of the catalysts becomes shorter as the temperature increases. The maximum temperature used is not particularly critical, but should be below the temperature at which substantial decomposition of the reactants or products occurs. For example azobisisobutyronitrile has a Halbujertzeit of 6 minutes at 100 ⁰ C..

In the case of the preparation of the polymer / polyols according to the invention Applied l / experienced, the monomers in the polyol are polymerized. Usually the monomers are soluble in the polyol. It has been found that the dissolution of the monomers first in a little Proportion of the polyol and the addition of the solution thus formed to the remaining polyol at the reaction temperature, the mixing of Monomers and polyol eases and fouling the reactor can reduce or eliminate. If the monomers are not soluble in the polyols, known methods such as dissolving can be used of the insoluble monomers in another solvent, for dis-

609813 / 09U

Pergieren the f'.onomeren in the polyol can be used before the polymerization. The conversion of monomers to polymers by this process is remarkably high (e.g., monomer conversions of 85-95 % are usually achieved).

The ratio of acrylonitrile to styrene around polymers is always slightly below the ratio of acrylonitrile to styrene monomers in the feed because the styrene usually reacts slightly faster than the acrylonitrile. Are e.g. acrylonitrile and styrene monomers introduced in a weight ratio of 80:20, then would have the polymer obtained has an acrylonitrile: styrene weight ratio from about 79:21 to 78:22.

Although the present invention is based on the use of a monomeric Acrylonitrile-styrene system is directed, of course small amounts of one or more additional monomers can also be used. In this case, however, should the relative amount of acrylonitrile remain within the limits given above.

The polymer / polyol preparations according to the invention are new and are characterized by a relatively high concentration of small polymer particles, so that practically all polymer particles are below about 30 microns, as shown by their ability, practically completely, ie more than 99% by weight , one after the other Pass through a 150 mesh wire screen with average mesh openings of about 105 microns and a 700 mesh wire screen with average mesh openings of about 30 microns when diluted with isopropanol to reduce viscosity (470 g preparation and 940 g isopropanol). Usually the average size of the polymer particles is less than about 1 micron.

8C8813 / 09U -. "

The polymers in the polymer / polyol preparations according to the invention lie as discrete polymer particles and relatively / small agglomerates from the convergence of two or more discrete particles and agglomerates in the polymer polymers. The term "particle size" as used herein refers to the numerical average size of these discrete particles and agglomerates. The polymer / polyols are free from large polymer particles (large ones formed by the convergence of many discrete particles Grains) in an amount that would affect the manufacture, handling and use of the polymer / polyols.

The polymers / polyols according to the invention are stable dispersions, so that practically all of the polymer particles on standing for extended periods of several months without any noticeable mark remain dispersed upon settling. This stability of the product is also due to the relatively small amount of material (Cake), which is drawn from the samples in laboratory centrifuges. However, the amount of cake formed is one Function of the molecular weight of the polyol. The cake appears when the tube is turned upside down and the free polyol is allowed to drain will; it is not made entirely of polymers, but also contains some trapped polyol.

The present invention also provides new elastomeric polyurethanes, which are produced by (a) a Polymer / polyol preparation and (b) an organic polyisocyanate in the presence of (c) a catalyst for the reaction of (a) and (b) reacts to form the polyurethane. The reaction can in any suitable manner, e.g. by the prepolymer or

609813 / 09U

take place,
one-shot process / If the polyurethane is a foam, the reaction mixture also contains a blowing agent and usually a foam stabilizer. If the polyurethane is a solid or microcellular elastomer, the reaction mixture can also contain chain extenders.

The organic polyisocyanates suitable for producing the polyurethanes according to the invention are organic compounds which contain at least two isocyanate groups. These compounds are known in polyurethane foam production. Suitable organic polyisocyanates include the carbon diisocyanates _; for example alkylene and arylene diisocyanates, such as the known triisocyanates and polymethylene-poly-phenyl isocyanates). Suitable polyisocyanates are, for example, 1,2-diisocyanatoethane, 1,4-diisocyanatobutane, 2,4-diisocyanatotoluene, 2,6-diisocyanatotolylene, 1,3-diisocyanato-o-xylene, 1,3-diisocyanato-m-xylene, 1, 3-diisocyanate-p-xylene, 2,4-diisocyanato-i-chlorobenzene, 2,4-diisocyanate-1-nitrobenzene, 2,5-diisocyanate-i-nitrobenzene, 4,4'-diphenylmethylene diisocyanate; 3,3'-Diphenylmethylene diisocyanate and polymethylene poly (phenylene isocyanates) of the formula:

NCO

in which χ has an average value of 1.1 to 5, preferably 2.0-3.0.

609813/0914

The catalysts suitable for the production of polyurethanes according to the invention include tertiary amines, bis (dimethylaminoethyl) ether, trimethylamine, triethylamine, W-methylmcrpholine, [■ I-ethylmorphaline, N, W-dimethylethanolamine, N ·. N -M 'j tf' -Tetramethyl-1,3-butenediamine, triethanolamine, 1,4-azabicyclo- / 2.2.2 / -octane, pyridine oxide, etc., and organotin compounds such as dialkyltin salts of carboxylic acid} · ^ z. B. dibutyltin diacetate> dibutyltin dilaurate, dibutyltin _maleate} dilauryltin diacetate, dioctyltin diacetate, etc. A trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide or dialkyltin dichloride can also be used. Such compounds include Z = B. Trimethyltin hydroxide, tributyltin hydroxide, tructyltin hydroxide, dibutyltin oxide, dioctyltin dichloride, etc. The catalysts are used in small amounts, for example from about 0.001-5 % by weight, based on the weight of the reaction mixture.

The blowing agents suitable for producing the polyurethane foams according to the invention include water and halogenated hydrocarbons, such as trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dichloromethane, trichloromethane, 1,1-dichloro-1-fluoroethane, 1,1,2-trichloro-i ^^ - trifluoromethane, hexafluorobutane , Uctafluorcyclobutane, etc. Another class of blowing agents includes thermally unstable compounds which release gases when heated, such as N, N ¹ -dimethyl-N, N'-dinitrosoterephthalamide, etc. A preferred foaming process for making flexible foams is usually the use of water or a Combination of water plus a fluorocarbon blowing agent such as trichloromonofluoromethane. The amount of blowing agent used varies with factors such as that in the foamed product

6Ü981 3 / 091A

- 19 desired density.

Those suitable for producing the polyurethane foams according to the invention Foam stabilizers include "hydrolyzable" polysiloxane-polyoxyalkylene block copolymers, e.g. the block copolymers of US PSS 2,834,748 and 2,917,480 suitable class of foam stabilizers are the "non-hydrolyzable" Polysiloxane-polyoxyalkylene block copolymers, such as the block copolymers of US PS 3,505,377, the U.S. Patent Application 888 067 dated Dec. 24, 1969 and the Br PS 1,220,471.

The microcellular poly-

(Chain extension agent)

Suitable extenders for urethane elastomer include aromatic polyamines and aromatic glycols. Suitable hindered aromatic polyamines are, for example 3-chloro-4,4 ^{1-diaminodiphenylmethane,} 4,4'-Hethylen-bis- (2-chloroaniline), Cumoldiamin, toluenediamine and dichlorobenzidine. Suitable aromatic glycols are the reaction products of alkylene oxides with aromatic amines or alcohols with zujei active hydrogen atoms, in particular the reaction products of alkylene oxides with di (hydroxyalkoxy) aryl compounds and primary aminoaryl compounds. The preferred aromatic glycols are the reaction products of ethylene oxide and aniline. Other extenders include ethylene oxide and propylene oxide adducts of bisphenol A ("Pluracol-P-245") or the propylene oxide adducts of aniline ( ¹¹ C-100 "). Other suitable extenders are butanediol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc. .

6 0 9813/0914

The polyurethanes produced according to the invention are suitable for Purposes in which the polyurethanes made from conventional polymer / polyol preparations are used; they are special suitable as armrests, bumper pads, mattresses and automobile bumpers.

The following examples illustrate the present invention, without restricting them »The following terms, symbols and abbreviations are used:

"Theoretical molecular weight" of a polyol means a molecular weight calculated using equation (A) above

Functionality of the
on the basis of the starting materials used to produce the polyol and the experimentally determined hydroxyl number of the polyol.

Refers to "Experimental Molecular Weight" of the polyol refers to a molecular weight calculated using the above equation (A) based on that determined experimentally Functionality and hydroxyl number of the polyol.

The "molecular weight" of the polyols is either theoretical or experimental number average molecular weight.

"Triol" or ⁿ diol "means the nominal functionality of a polyol based on the functionality of the parent compound. The actual polyol functionalities are somewhat lower (3-20 % lower) than the nominal functionality due to the presence of some amount of lower material

609813/0914

Functionality that is formed by side reactions. These Mebenra actions are all the more noticeable the higher the molecular weight of the polyol produced.

"Polyol I" is a polyalkylene oxide triol made from propylene and ethylene oxides and glycerol has a theoretical number average molecular weight of 5000 and an experimental number average molecular weight of about 4,300. The alkylene oxide units are mainly present in blocks and the primary OH content is approximately 75 %. The ethylene oxide is used to "cap" the triol. On the basis of his Alkylenoxidgehaltes this triol contains • 85 Gbw .-% C ₃ H ₆ O and 15 wt -.% C ₃ H ₄ O.

"Polyol II" is a polypropylene oxide triol made from propylene oxide and glycerin with a theoretical number average Molecular weight of about 3000.

"Polyol III" is a polypropylene oxide triol made from propylene oxide and glycerin having a theoretical number average molecular weight of about 5,000 and an analytical one determined number average molecular weight of about 4200.

"Polyol IU" is a polypropylene oxide triol made from propylene oxide and glycerin having a theoretical number average molecular weight of about 6,000.

6 09813 / 09U

"Polyol U" is a polypropylene oxide diol made from propylene oxide and dipropylene glycol having a theoretical number average molecular weight of about 1,000.

"Polyol UI" is a polypropylene oxide diol made from propyl oxide and dipropylene glycol with a theoretical number average f-molecular weight from etuua 2000.

"Polyol VII" is a polypropylene oxide diol made from propylene oxide and dipropylene glycol having a theoretical number average molecular weight of around 3000.

"Polyol Ulli" is a palypropylene oxide triol made from propylene oxide And glycerin with a hydroxyl number of 650.

"A / S" or "A: S" means the weight ratio of acrylonitrile to styrene.

"Poly A" means polyacrylonitrile, "Poly S" means polystyrene. "TDI ¹¹ is a mixture of 80 % 2,4-tolylene diisocyanate and 20 % 2,6-tolylene diisocyanate." VAZO-64 "or" UAZO "means 2,2'-azobisisobutyronitrile. * Means that this is a comparative example and Unless otherwise indicated, all parts and percentages are Geui. parts and ^

Filterability

The preparations according to the invention are practically free from polymer particles with diameters greater than 30 microns. The preparation meets these criteria if more than 99 parts of the same are done one after the other pass a 150 mesh and 700 mesh sieve in the following test:

609813 / 09U

2538118

- 23 A 470 g sample of the preparation to be tested was mixed with 940 g isopropanol diluted to reduce viscosity. The diluted

2 sample was passed through a 150 mesh sieve of 15.5 cm and then passed through a similar 700 mesh screen. (The sieves are cleaned, dried and geu / ogen ujorden before the test. '). then The sieves were used to remove any polyol using isopropanol washed, dried and bent. The difference between the final and initial sieve weight corresponds to the amount of polymer, that didn't go through the sieve. The 150 mesh screen has 105 microns and square average mesh openings is a "Standard Tyler" 150 square mesh screen. The 700 mesh sieve is from a Dutch body shape with average mesh openings of 30 microns and published in "Bulletin 46267-R" of Ronningen-Petter Comp., Kalamazzo, Me., Described.

Centrifugable solids

The polymer / polyol preparation lasted for about 24 hours at about 3000 Rev./min and a radial centrifugal force "g" of 1470 ezentrifugisrt. Then the centrifuge tube was inverted and 4 hours expired. The non-flowing cake remaining at the bottom of the tube is expressed as Ji by weight of the initial weight of the tested preparation indicated.

Example 1 to 47

Examples 1 to 46 were carried out continuously in one with baffle plates and impeller equipped tank reactor. The feed components were continuously pumped to the bottom of the reactor after having a mixer installed in series to ensure complete hischens the feed components before entering the

609813/0914

Had passed through the reactor. The internal reactor temperature was precisely controlled to 1 ° C. by regulated heating or cooling outside the reactor. The contents of the reactor were stirred thoroughly. The product from the top of the reactor flowed continuously through a back pressure regulator. This mar adjusted to give the reactor a certain positive back pressure. The product then flowed through a water-cooled tubular heat exchanger to the product receptacle. Shares the crude product was vacuum stripped at 2 mm pressure and 120-130 ⁰ C. for testing. Conversions were determined from analysis of the amount of unreacted monomers present in the crude product prior to stripping. In Run 47, the product from the reactor head was further heated in a second reactor to increase the conversion of monomers to polymer.

The experimental conditions and results of Examples 1-47 are summarized in Tables A to H below. Since 100 % of the preparations prepared in Examples 1-40 and 43-47 passed through the 150 mesh screen in the filterability test, only the percentage passed through the mesh screen is shown in Tables A through H.

609813 / 09U

Table A.

α co oo

example

Reaction temp .; ⁰ C. Weight # "VAZO" in charge. Monom.go.infeed .; Acrylonitrile by weight: styrene ratio Polyol feed rate; g / h polyol ■ Monom.it.cH.g .;

Calculate polymer in product »; Poly A %

Poly s. Fi overall; fo A / S ratio

Product properties _n

Visc. (HoeppTer) at 25 C; cps.

Filterability by 700 mesh centrifugal solids; %

g / h

l (a) * 120.5 ■ 3; 4th 5 * 6 * Zl 120.5 0.39 120 120 120 120 120 0.39 30.3 0.40 0.40 0.39 0.40 0.41 30.4 85/15 30.6 31.2 30.4 31.3 31.5 90/10 1898 80/20 75/25 70/30 65/35 60/40 1904 I. 1888 1880 1956 1900 1866 I. 824 I. I. I. I. I. 832 23.8 832 852 856 864 858 23.1 4.5 22.8 21.8 19.8 • 18.8 17.3 3.1 28.3 6.0 7.7 9.0 10.8 '12.4 26.2 84/16 28.8 29.5 28.8 29.6 20.7 88/12 .2,965 79/21 74/26 69/31 63/37 58/42 8,968 100 2., 828 3.365 3.143 3.424 3.728 2.8 3.19 100 100 33.4 9.8 7.0 50.3 2.65 4.17 5.63 8.22 7.39

(a) Experiment ended, but reactor clogged with sludge-like precipitation
* not according to the invention, but comparative example

Table B. example

Reaction temp .; ⁰ C. wt. 56 "VAZO" in charge. Monomer.go. in charge .; Weight %

Acrylonitrile / styrene ratio polyol charge speed; g / h σ »polyol

Monomer feed.speed; Calculate g / h of polymer in the product .; Poly A, fi poly S, fo overall; $ A / S ratio

Product features

Viscosity (Hoeppler) at 25 C .; cps, filterability; $ by 700 mesh centrifugal solids; i>

O CO OO

120

0.41

23.8

80/20

2020

631

17.1 4.6 21.7 79/21

2.008

100

2.0

120

0.40

25.9

I 712

18.9 5.0 23.9 79/21

.2,105

100

1.9

0.41 31.4

946 *

23.6 6.2 29.8 79/21

3.150

11

130

0.40

35.8

894

498

27.4 7.1 34.5 79/21

4,240

100

3.1

130

0.40

40.8

812

560

31.4 8.1 39.5 79/21

6.434

100

4.2

11

129.9

0.40

46.2

744

640

35.6 9.3 44.9 79/21

12,282

100

4.8

cn to 00

Table C. example

Reaction tempi; ^ c. Wt .- ^ "7AZO ¹ 'in charge. Monomer go, in charge; wt .- # acrylonitrile: styrene ratio polyor charge, rate; g / h polyol

Monomer feed.speed; g / h of polymer in the product

calculate - poly A, $ poly S, overall; % A / S ratio

Product properties Viscosity (Hoeppler) "at 25 C; cps. Filterability; $ through 700 mesh centrifugal solids; $

15 *

16

17 (a) *

18th

120 120.5 120.5 120.5 120 0.40 0.41 0.40 0.40 0.39 22.2 27.5 27.3 26.9 21.8 50/50 50/50 80/20 90/10 90/10 2180 1988 2000: 2052 • 2212 III III III . III. III 624 754 752 756 618 9.9 12.4 20.5 21.6 17.5 10.5 13.2 5.4 2.7 2.1 20.4 25.6 25.9 24.3 19.6 48/52 48/52 ■ 79/21 89/11 89/11 2.053 2.809 2,498 7.212 4.032 . 100 0.6 100 11.5 100 7.3 ■ 12.4 2.58 66.8 49.7

(a) poor operation; the reactor tended to plug

Table D. example

Reaction temp .; ⁰ C. Weight fo "YAZO" in charge. Monomer content in feed .; G-ew. -% acrylonitrile: styrene ratio polyol charge speed; g / hr polyol

Monomer feed.speed; g / h of polymer in the product

calc. Poly A, $> Poly S, £

all in all; $

A / S ratio product characteristics

Yiskos. (Hoeppler) at 25 ⁰ C .; cps.

Filterability .; # through 700 mesh centrifugal solids; #

20th

21

22 *

23 *

120 120 120 120 - 120 0.41 0.41 0.42 0.40 0.42 21.5 21.5 21.9 21.1 21.9 90/10 80/20 70/30 60/40 50/50 2160 2128 2050 2068 2092 II II II • II II 592 589 578 554 588 16.6 15.4 13.6 11.1 9.5 2.1 4.2 6.3 8.0 10.3 18.7 19.6 19.9 19.1 19.8 89/11 79/21 68/32 58/42 48/52 2.616 1.082 1,200 1.238 1,549 67 100 100 6th 0.6 57.7 4.4 8.6 10.4 22.3

Table E. example

Reaction rates; C. Weight # "YAZO" in charge. Monomer housing in feeder j Acrylonitrile / Styro1-Yrehaltni s Polyorbeschick.geschw .; g / h Polyol Monomerbesohigh.spw .; g / h of polymer in the product

calc. Poly A, # Poly S, $>

all in all; #

A / S ratio product characteristics

Viscous. (Hoeppler) at 25 ⁰ C.

Filterability; jt> by Zentrlfug. Pesticides; $

25 *

26 *

27 *

cps. mesh

120 120 120 120 0.41 0.40 0.41 0.44 18.3 18.1 ■ 13.4 8.7 90/10 50/50 .50 / 50 50/50 2244 2264 2352 2366 II II Il II 503 500 363 226 14.4 7.6 5.3 3.2 1.7 8.2 5.8 3.8 16.1 15.8 11.1 7.0 89/11 48/52 48/52 46/54 1.497 948 823 726 100 14th 100 100 40.9 12.7 6.2 1.5

Table! F example

Reaction temp *; ⁰ C.

Weight .- ^ "YAZO" in charge.

Monomer go, in charge .; Acrylni t ri 1 / Styro l- »Ratni s Polyol feed speed; g / h polyol monomer feed rate; g / h Polymer in the product

calc. Poly A, # poly S, %

all in all; $>

A / S ratio of pro duct specifically ften cha

Viksosit. (Hoeppler) at 25 ⁰ C .; cps, filterability; $> by 700 mesh centrifug. Solids; $>

29 *

30 *

120 120 130 0.40 0.40 0.41 25.9 31.2 36.5 80/20 80/20 80/20 2004 1897 876 VII VII • VII 702 860 512 18.7 23.0 28.1 5.0 6.1 7.3 23.7 29.1 35.4 79/21 79! / 21 79/21 1,549 2.112 3.447 100 36 6.2 3.7 10.1 13.3

11 *

120

0.41

27.6

70/30

1980

VII

754

17.3 8.0 25.3 68/32 V

1.927

1.9

14.3

K? cn to

Table G. example

Reaction temp .; ⁰ C.

Weight .- ^ VAZO in charge.

Monomgrgeh. in charge weight # Acrylonitrile / styrene ratio polyol charge speed; g / hr polyol

Monomer feed.speed; g / h

Polymer in the product TaBr ₉ Poly A, fo Poly S, #. all in all; $> A / S ratio of product properties visc. (Hoeppler) "at 25 ⁰ O .; cps. Filterability; # through 700 mesh centrifugal solids; $>

33

120

0.39

25.6

35 36 (a) * 37 * 38 * 39 40

120

0.41

26.5

120.5 120
0.40 0.39
20.1 16.6

85/15 80/20 70/30 80/20 50/50
2060 2056 2014 2248 2232
VI VI VI VI VI
732 708 726 564 444

20.0 18.6 16.8 14.0 6.7
3.8 5.0 7.7 3.8 7.4
23.8 23.6 24.5 17.8 14.1
84/16 79/21 69/31 79/21 48/52

120 120 120 120

0.40 0.43 0.41 0.44

12.2 7.5 17.4 7-7

50/50 50/50 90/10 90/10

2386 2576 2272 2550

VI VI VI VI

332 208 478 214

4.5 2.3 13.0 5.1 5.1 2.8 1.6 .7

9.6 5.1 14.6 5.8 47/53 45/55 89/11 88/12

926 853 I, 156 637 1245 667 668 741 422 100 100 1 100 0.6 26.6 100 100 100 13.4 9.8 25th .6 6.9 58.2 42.4 44.6 29.6 0.9

(a) Reactor clogged, attempt not ended.

σι σ co co

example

Reaction temp .; ⁰ C.

Wt .- # "VAZO) in charge.

Monomers go, in charge .; Wt% Acrylonitrile: styrene ratio polyol charge speed; g / h Polyol monomer feed rate; g / h of polymer in the product

- Poly A, % Poly S,%

all in all

A / S ratio product characteristics

Viscous. (Hoeppler) at 25 ⁰ C; cps, filter bar; % by 700 mesh centrifug. Solids; %

(a) Reactor clogged, attempt not ended

(b) Product separated on standing

(c) two stages

Tabel H 44 45 * 46 * 47 (c) 2713 1904 X \ 253 42 (b) * 43 * 120 120 120 120 100 I. I. co 120 120 120 0.40 0.40 0.40 0.41 4.1 866 0.39 0.44 0.40 27.3 27.1 22.5 31.3 24.1 25.5 7.7 26.8 80/20 90/10 50/50 80/20 6.2 80/20 80/20 50/50 2024 2046 2112 30.-3 < 2054 2498 2092 IV IV IV 79/21 ' V V IV 758 760 612 2868 708 210 766 20.3 ' 21.5 10.0 100 12.0 5.3 2.7 10.7 3.1 12.9 25.6 24.2 20.7 24.9 79/21 89/11 48/52 48/52 3358 9680 3461 100 3.4 2.9 2.3 49.6 .A Ö1 "1 A AT" 6.3 eenciex.

253811B

B is ρ ie 1 48 to 5 4

In these examples, a stirrer and baffle tank reactor was used which was pressurized to reduce the volatilization of the monomers; thus the reactor was fitted with a back pressure valve. It was operated continuously and its contents were thoroughly stirred. Polyol I was used. The remaining iionomeren in the product were determined and stripped under vacuum at 120-13O ⁰ C. before the product on viscosity Usui. has been analyzed. The additional reaction conditions were 120 ° C., 0.5% by weight catalyst and 32 % by weight monomer in the feed. The findings regarding the individual examples were as follows:

Example 48 ; this example was not ended due to the high product viscosity and the high solids content in the product, which clog the outflow of the back pressure valve. No equilibrium conditions were achieved. Before the end of the experiment, only a small amount of product was collected, from which a small sample was stripped and analyzed. Example 49 ; The flow of raw materials and product was interrupted long enough to clear the Example 48 back pressure valve. Example 49 was started with an A / S ratio of 90-10. The reactor was only opened after Example 50. The product from the conditions of Example 49 does not seem good ("seedy"). Example 50 ; Without interrupting the flow of starting materials and product, the conomer ratio was changed to 80:20. An obvious improvement was seen in the product, which was all the more surprising when one thought of the heavy polymer build-up which was evident in the reactor when it was opened according to Example 50.

609813/0914

The reactor was found to be half filled with a polymer sludge on the ground, which probably during example 48 and possibly Example 49 was formed. The reactor was according to example

50 cleaned.

Example 5'i to 54: These examples were carried out without interruption. The operation was good without any problem

Polymer accumulation

The test conditions and results of Examples 48-54 are listed in Tables I and 3 below.

609813 / 09U

Table I. example

Acrylonitrile / styrene ratio reaction temp .; C. Weight 96 "VAZO" in charge. Monomer go, in charge .; Weight - 96

Polyol I feed rate; g / h Monomer feed.speed; g / h

48 * 100/0

49 *

50 *

51

52 *

53 *

54 *

90/10
121
0.48
28.6 80/20
120
0.53
31.6 80/20
120
0.53
31.9 70/30
120
0.56
33.7 57/43
120
0.54
32.6 50/50
120
0.55
32.7 2124
849 1812
836 1744
816- 1772
900 1760
852 1748
848 • «J.

example

total calculated% poly A in the product total calculated% poly S in the product total calculated% polymer in the product A / S ratio total in the polymer % Poly A in the product in total % p & iy S in the product total % Polymer in the product

Product properties

Visc. (Hoeppler) at 25 ⁰ C; cps. Translucent ^, % (1)

500 m / u

600 m / rev color evaluation (2)

Sedimentation value; % (3) filterability (4) 150 mesh; Time

% Passage 700 mesh; Time, min

% Passage

Appearance of the sample bottle (6) Sedimentation rating (7)

48 *

27.0

27.0

9650 8583

Tabel J 51 52 * 53 * 54 * 49 * 50 * 24.0 22.2 17.4 15.1 23.5 23.7 6.3 10.0 13.7 15.9 2.9 6.2 30.3 32.2 31.1 31.0 26.4 29.9 79/21 69/31 56/44 49/51 89/11 79/21 22.7 20.5 18.5 15.6 22.2 23.4 6.5 8.8 13.0 14.3 2.9 6.3 29.2 29.3 31.5 29.9 25.1 29.7

2920

3365

3758

4877

5070

78 .8th 87. 5 74.2 73.4 61.6 55 .1 51 .7 81 89 4th 82.2 82.1 71.3 63 .8th 59 .1 6th 3 1-1 / 2 1-1 / 2 1-1 / 2 1 1

15.3 51.9

1.9

3.5

12.0

16.2

11 sec. 13 sec. 10 sec. 10 sec. 10 min. 10 min.

_- 100 100 100 100 32 10 N) 20th ¹⁰ / ^ 2.8 20th 11.6 10 Cn - 46.6 41.7 ( ⁵ > 100 89 0.9 2.8 2 3 2 1 2 4th 4th 3 9 3 1 2 7th 7th

In the above table J mean

(1) 0.01 % polymer in Polyol II diluent

(2) 1 = brightest; 6 = darkest

(3) by centrifuge test

(4) Sample diluted 2: 1 with isopropanol

(5) The low value probably results from transferred material from Examples 48 and 49

(6) 0 = clear; 5 = whitish residue

(7) sediment in sample bottle; 0 = none; 8 = more continuous white cake

609813/091 A

$ 253811

For further explanation, the usable ranges of the polymer content (wt .-% f-ionomers) and the acrylonitrile: styrene ratios of the preparations of the examples and of other polymer / polyol preparations for polyols with different molecular weights are shown in the accompanying drawings. The numbers next to the data points in these drawings relate to the preparations produced in the correspondingly numbered examples; the symbol "X" denotes a polymer / polyol preparation which does not correspond to any of the numbered examples.

In the drawings, the preparation produced according to Example HI-D of US Pat. No. 3,832,201 is shown as "HI-D", the preparation described according to Example WII of US Pat. No. 3,832,201 as "Uli", which is described in Example 4-V from Belgium Patent Specification 788 155 as "4-V", the preparation prepared in Example 1 of GB PS 1 321 679 as "BPS-1" and the preparation prepared in Example 4 of GB PS 1 321 679 as "BSP-4 ¹¹ designated.

In Figs. 4, 8, 9, 10 and 11, the dashed areas A, B,. C, D and E preparation with such a mutual relationship of A: S, polymer content and polyol molecular weight that one of the invention improved polymer / polyol preparations. FIG. 10 is a summary of that shown in FIGS. 4, 8 and 9 Limit values.

In Figs. 4, 8 and 9 define the areas below the dashed line Area and curve preparations with satisfactory Properties, but without the critical mutual relationship of properties. The same goes for the area below the lower curve in Figs. 10 and 11.

609813 / 09U

2538118

Figures 1 through 3 are graphical representations of the data from Examples 1 through 7 (summarized in Table A) and show the effect of varying the acrylonitrile: styrene ratio (A: S) between 90:10 and 60:40 with a monomer content of Loaded about 31 % and with Polyol I (molecular weight 5000). As shown in Figure 1, there is a sharp increase in the percentage of product that passes through a 700 mesh screen at A: 5 ratios of 85:15, 80:20 and 75:25. According to FIG. 2 there was a minimum of percent centrifugable solids and according to FIG. 3 there was a minimum of viscosity at an A: S ratio of 80:20.

Figure 4 is a graphical representation of the data from Examples 8-13 (summarized in Table B) and shows the effect of increasing the monomer content in the feed at an A: S ratio of 80:20 and with polyol I. As in FIG As shown in Figure 4, when the percent conomer in the feed was increased to 46 % , the product passed through a 700 mesh sieve completely (at 100 / g) * There was a relatively small increase in centrifugable solids. Product viscosity increased with polymer content, but is at a minimum for a given polymer content by using an A: S ratio of 80:20.

Fig. 4 also shows the curve from Example 14-18 (summarized in Table C), ωό in contrast to that used in Example 1-13 Polyol with terminal ethylene oxide groups (polyol i) Polyol (Polyol III) consisting entirely of topylene oxide is used became.

609813/091 L

Figures 5 through 8 are graphical representations of the data from Examples 19-23 (summarized in Table D) and show the effect of varying the A: S ratio between 90:10 and 50:50 at a monomer content of about 21 % with Polyol II , which is a propylene oxide-only polyol with a molecular weight of about 3000. There were maximum percentages of material passing through 700 mesh sieve (Figure 5) and minimums of centrifugable solids (Figure 6) and product viscosity (Figure 7).

Figure 8 is also a graphical representation of the data from Examples 24-27 (summarized in Table B) and aids in that Definition of the limits of the A: S ratio and polymer content for polyol II.

Figure 8 is also a plot of the data from Examples 28-31 (summarized in Table F) and shows a diol having a molecular weight of 3000 (Polyol VIl) against the triol used in Example 19-27 with a molecular weight of 3000 (Polyol II).

Figure 9 is a plot of the data from Example 32-40 (summarized in Table G), which were carried out using a diol with a molecular weight of 2000 (Polyol VI).

Examples 41 and 42 (summarized in Table H) show that the use of a diol with a molecular weight of 1000 (polyol V) not to form an improved polymer / polyol preparation leads, as it is from the use of a polyol with a molecular weight of at least 1500 according to the invention Demand is achieved.

609813/0914

2538178

- Examples 43 to 46 (summarized in Table H)

show the use of a particularly high molecular weight polyol (Polyol IU).

Figures 10 and 11 define the percentage of monomer and polyol molecular weight, those relating to the improved preparations according to the invention to lead. Hit reference to Fig. 10 are the inventive, Preparations made from relatively low molecular weight polyols (e.g. polyols with a molecular weight of 1500-2500) in equal measure to preparations which were obtained from such polyols, but using A: S ratios not according to the invention, relatively stable. Referring to Figures 10 and 11, the present invention, made from relatively high molecular weight polyols (e.g., those preparations made with molecular weights of at least 4500 and preferably 4500-12000) compared to those, those from these polyols, but not according to the invention when used A: 5 ratios produced, relatively less "waste" and lower viscosities. These latter improvements are particularly evident at A: S ratios of 80:20. Furthermore, those from such give higher molecular weight polyols manufactured preparations polyurethanes with improved elongation and tear resistance.

Example 55 to 72

These examples were made to compare the properties of polyurethane elastomers made from known polymer / polyol preparations (Example 55-65) with the properties of polyurethane elastomers, produced from polymer / polyol preparations according to the invention Example 66-72). Those used in Example 55-65

609613/0914

- 42 -

Polymer / polyols were made from Polyol I and had the in Polymer composition shown in Table K. The polymer / polyols used in Examples 66-72 are according to the examples above 8, 9, 3, 10, 1-1, 12 and 13 have been made.

The polyurethane elastomers were made from the following starting materials:
Mate r ial amount

Polymer / polyol 1.0 equivalent

Quasi-prepolymer (1) 2.1 equivalents

Extender (2) 1.0 equivalent

Stannous octoate 0.05 parts

(1) = reaction product of 7 moles of TDl and -1 mole of polyol VIII with

30.7 wt -.% Free isocyanate groups

(2) = reaction product of 2.4 mol of ethylene oxide and 1 mol of aniline

with a hydroxyl number of 565

The polymer / polyol, "extender", and catalyst were placed in a 500 cc four-necked flask equipped with a stirrer, thermometer, vacuum inlet, and heating mantle. This mixture was degassed (vacuum pump, et ω a 1.0 mm Hg) for 30 minutes at 45-45 ° C., the vacuum was released and the quasi-prepolymer was added. Then, again 30 seconds uiurde a vacuum is applied and the thus-formed liquid mixture in heated at about 4O ⁰ C. glass molds cast which were kill previously coated with a mold release agent "Hysol". The molds were then clamped together and the elastomer at 100 ° C for 16 hours. cured in an oven.

609813/0914

2538118

The physical properties of the polyurethane elastomers produced in this way are summarized in Table K below. The properties of the preparations with A: S ratios of 50:50 and 80:20 for a given polymer content are comparable. However, the former preparations were often difficult to manufacture and use due to the formation of large grains.

609813/0914

• Table K

example

55 * 56 * 57 * 58 * 59 * 60 * 61 * 62 * 63 *

Weight -% Polyacrylonitrile; referring to urethane 0.0 10.51 14.21 15.32 18.77 23.76 -

with reference to polymer / polyol 0.0 12.8 17.2 18.35 22.4 28.0

CO 50:50
re A: S polymer; Wt%
.a. urethane "-ν re . on polymer / polyol O
εο 80:20 A: S polymer; Wt% ** re .a. urethane re . on polymer / polyol

physical properties (l) Shore A hardness 100% modulus; psi

Tensile strength .; psi elongation; %

Tear strength Nozzle "C", pli - - ■ -

(1) ASTM D-3196-73T for Example 55-6θ and ASTM D-M2 for Example 61 and? 2

0.0 —— —— —— —— —— 0.0 - - - - 0.0 __ 0.0 - - - - - 50 68 73 __ __ 83 180 352 400 450 545 1075 188
177 435
160 580 '
130 745
147 1455
• 180 1650
145 11.5 14.1 at the 62 353 644
157

91

378

596

147

82

67

526 '832 ^

82

Table K continued example

64 * 65 * 68 69 .70 71

CO (DO

25.96 28.46 - 30.0 33.9

% By weight polyacrylonitrile based on urethane

based on polymer / polyol

50:50 A: S polymer; Weight_% related to urethane

based on polymer / polyol

80:20 A: S polymer; Wt% based on urethane based on polymer / polyol

physical properties Shore A hardness

100 % modulus; psi

Tensile strength psi elongation; %

Tear strength Nozzle "C", pii (2) 100% module extrapolated from the stress strain curve

71 77 68 745 1119 484 794
103 1711
133 685
122 112 139 119

18.24 20.2 24.5 24.9 29 21.7 24 28.8 29.8 34.6

74 75 81

795 790 1340

795 1083 1116

100 120 83

126 149 152

34.2 38.9 * 39.6 44.7

79 1165 2800

969 2667

83 95 i °°

119 168 - ±

Claims (10)

- 46 patent claims e J- Liquid polymer / polyol preparations, essentially consisting from (1) 45-90 Gem .- / o of a polyoxypropylene polyol with a i ^ molecular weight of at least 1500 and (2) 55-10 Geuj .- ^ o one Acrylonitrile-styrene polymer, which essentially consists of (a) 60-90 Geiu.-Jä polymerized acrylonitrile and (b) 40-10 Gem .- ^ polymerized styrene consists, the polymer in the form of Stably dispersed in the polyol particles is present, the preparation is practically free of polymer particles with a diameter over 30 microns and this is made by polymerizing a monomeric mixture of acrylonitrile and styrene in the polyol u / orden is. 2.- A preparation according to claim 1, characterized in that the polyol has a molecular weight of about 5000 and (i) the percentage by weight the monomer mixture, based on the sum of the weights of the used to manufacture the preparation Mixture and the polyol, and (ü) the weight ratio of Acrylonitrile to styrene in the monomeric mixture are such that a curve from (i) against (ii) falls within region A of FIG. 3.- A preparation according to claim 1, characterized in that the polyol has a molecular weight of about 3000 and (i) the percentage by weight the monomer mixture, based on the sum of the weights of the mixture used to produce the preparation and the polyol, and (ii) the weight ratio of acrylonitrile to styrene in the monomeric mixture are such that a curve from (i) against (ii) falls into region B of FIG. 8, with the proviso that this preparation is different from one in which a curve from (i) against (ii) to point 4-U or Uli 609813 / 09U this area falls. 4. ~ preparation according to claim 1, characterized in that the polyol has a molecular weight of about 2G00 and (i) the weight percentage the monomer mixture, based on the sum of the weight of the mixture used to produce the preparation and the polyol, and (ii) the weight ratio of Acrylonitrile to styrene in the monomeric mixture are such that a curve from (i) against (ii) falls into region C of FIG. 5.- A preparation according to claim 1, characterized in that the (i) percentage by weight of the monomeric mixture, based on the sum of the weight of the mixture used to produce the preparation and the polyol, and (ii) the molecular weight of the polyol are such that a curve from (i) against (ii) falls in the area D of FIG. 10, with the proviso that this preparation is different from one whose curve from (i) against (ii) at point 4-V, point Uli, BPS-1 and point _B PS-4 of this area falls. 6.- preparation according to claim 1, characterized in that (i) the Geojicht percentage of the monomeric mixture, based on the Sum of the weights of the mixture used to produce the preparation and of the polyol, and (ii) the molecular weight of the polyol are such that a curve from (i) against (ii) falls within region E of FIG. 7.- preparation according to claim 1, characterized in that it consists essentially of 45-75 wt .-> o polyol and 55-25 Geuu-yi polymer consists. 609813/0914 8, - preparation according to claim 1 and 5, characterized in that,
that the polyol has a molecular weight of 1500-2500. 9.- preparation -according to claim 1, characterized in that the Polyol has a molecular weight of at least 4500, preferably 4500-1200Ü. 10.- Process for the production of elastomeric polyurethanes, thereby characterized in that (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) to form the polyurethane. The patent attorney: 609813/0914