DE2242476A1 - POLYMER / POLYOL COMPOUNDS, PROCESS FOR THEIR MANUFACTURING AND THEIR USE FOR THE MANUFACTURING OF POLYURETHANE FOAMS - Google Patents

Description

PATENT LAWYERS 99/9/7 R

dr. W. Schalk dipl.-ing. P. "Wirth. Dip'l-ing. G. Dannenberg DR. V. SCHMIED-KOWARZIK · DR. P. WEINHOLD · DR. D. GUDEL

SK 6 PRANKFURT AW MAIN Q _aSQ G-8797-G

GH, ESCHENHEIMER STRASSE 39

UKIOF GARBIDE GORPOHAiPIOIi 270 Park Avenue

New York, N, Y. 10017 / USA

Polymer / polyol compositions, process for their preparation and their use for the production of polyurethane

• foam

3 0 9 811/112 3

The invention relates to polymer / polyol compositions and processes for their Manufacture and its use for the manufacture of polyurethane foams.

Polymer / polyol compounds used in the manufacture of polyurethane foams are known per se. Such compositions can be produced by polymerizing one or more olefinically unsaturated monomer, dissolved or dispersed in a polyol, in the presence of a free radical catalyst, these polymer / polyol compositions have the advantageous property that they Polyurethane foam made from it gives higher load-bearing properties than non-modified polyols.

^ ("load bearing properties")

The polymer / polyol compositions available commercially nowadays are primarily those compositions made from polyols and acrylonitrile or acrylonitrile / methyl methacrylate mixtures are. Such compositions are used industrially for the production of foams under such conditions in which the heat generated during foaming is easily dissipated (dissipated) (e.g. for the production of foams with a relatively thin cross-section), or under such conditions which generated relatively little heat during foaming will. An important source of heat in the formation of polyurethane foams is the reaction of water with the isocyanate groups and this reaction is often used to convert carbon dioxide produce, which foams the polyurethane. In these cases the density of the foam decreases and the amount of heat generated increases on) when an increasingly large amount of water is used. Know one of the commercial polymer / polyol compounds mentioned above is used under such conditions that the heat generated during foaming is not easily dissipated (e.g. when making a relatively thin sheet material), or under conditions such that one is used to produce a

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BATH ORIGINAL

Polyurethane foam having a density of less than O ₄ 028 grams / cm (1.75 lbs / ft ") is used sufficient quantity of water * the heat generated leads to a discoloration hz \ i * scorching (scorch) of the foam"

Polymers made from poly oils and acrylonitrile / styrene mixtures / Polyol compositions are also known (see Canadian patent specification 785 S35). Polyurethane foams foamed with water lower Density, which xverden produced from these masses, are subject to also the discoloration or scorching. The known process for the production of these masses is not entirely satisfactory » primarily because of the precipitation of large granules from the reaction mixtures Day no commercial success.

An object of the present invention is now to provide a method for Specify the production of polymer / polyol compositions that are used for the production of water-foamed polyurethane foams with a low density and less discoloration or »scorching

_t can be «

inclination used / Em Another object of the invention are the polymer / polyol compositions obtained and their use for production of water-foamed polyurethane foams with a low density, which have a lower tendency to discolour or scorch exhibit. Further objects, features and advantages of the invention emerge from the following description »

The invention is based on the fact that it has been found that polymer / polyol mass with improved properties by appropriate selection of the type and relative amounts of olefinic unsaturated monomers and by controlling the temperature used to prepare these compositions. Accordingly concerns

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BATH ORIGINAL

the present invention provides a method of making a flowable (liquid) polymer / polyol mass, which is characterized is that one

(1) 10 to 30 parts by weight "of a monomer mixture of (a) 50 to 75 parts by weight of acrylonitrile or methacrylonitrile I and (b) 25 to 50 wt -. \ Styrene or a-methyl styrene, always based on the total weight of these materials , dissolved or dispersed in

(2) 70 to 90% by weight of a normally liquid polyol - the Percentages of components (t) and (2) are based on the total weight sourced from monomer and polyol -

in the presence of a free radical catalyst in a Polymerized temperature at which the half life of the catalyst is not more than 6 minutes.

In the case of the preparation of the polymer / polyol compositions according to the invention Usable polyols can be a polyester with terminal hydroxyl groups, a polyhydroxyalkane, a polyphenol, a polyoxyalkylene polyol or the like. Among polyols that are used include one or more polyols of the following classes of compositions, either alone or in admixture, known to those skilled in the polyurethane field:

(a) alkylene oxide adducts of polyhydroxyalkanes,.

(b) polyesters with terminal hydroxyl groups,

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

(d) alkylene oxide adducts of phosphoric and polyphosphoric acids, (ο) alkylene oxide adducts of polyphenols,

(f) the polyols of natural oils, such as. B. Castor Oil and the like ......

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Examples of Mk-ylene oxide adducts of polyhydroxyalkanes are i.a. the alkylene oxide adducts of ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,4-, 1,5- and 1,6-dihydroxyjiexan, 1,2-, 1,3-, 1,4-, 1,6- and 1,8-dihydroxyoctane, 1,10-dihydroxydecane, glycerine, 1,2,4-trihydroxybutane, T, 2,6-trihydroxyhexane, 1,1, ί-trimethylolethane, T, 1,1-trimethylolpropane, Pentaerythritol, caprolactone, polycaprolactone ,. Xylitol, Arab it, Sorbitol, mannitol and the like, preferably the adducts of ethylene oxide, Propylene oxide, epoxybutane or mixtures thereof. A preferred one The class of alkylene oxide adducts of polyhydroxyalkanes are the ethylene oxide, propylene oxide, butylene oxide adducts or adduct units of trihydroxyalkanes.

Examples of polyesters with terminal hydroxyl groups are those which are prepared by polymerizing a lactone in the presence of an active hydrogen containing initiator, as described in U.S. Patent 2,914,556.

Another class of polyols that can be used are the alkylene oxide adducts of the non-reducing sugars in which the alkylene oxides have 2 to 4 carbon atoms. To the non-reducing Sugars and sugar derivatives include sucrose, alkyl glycosides, such as methyl glycoside, ethyl glycoside and the like., glycol glycosides, such as ethylene glycol glycoside, propylene glycol glycoside, Glycerine glycoside, 1,2,6-IIexanetriol glycoside. and the like., as well as the Alkylene oxide adducts of the alkyl glycosides as disclosed in US Pat. No. 3,073,788.

Another useful class of polyols are the polyphenols, and preferably the alkylene oxide adducts thereof, in which the alkylene oxides Have 2 to 4 carbon atoms. Examples of suitable polyphenols are bisphenol A, bisphenol F, condensation products of phenol and formaldehyde, novolak resins; Condensation products of various phenolic compounds and acrolein, the simplest representatives of this class are the 1,1,3-tris (hydroxyphenyl) propane, Condensation products of various phenolic

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BATH ORIGINAL

Compounds and glyoxal, glutaraldehyde and other dialdehydes, the simplest representatives of this class are the 1,1,2,2-tetrakis (hydroxyphenol) ethiines and the same.

Another useful class of polyols are the alkylene oxide adducts of phosphoric and polyphosphoric acids. Preferred alkylene oxides are ethylene oxide, 1,2-epoxypropane, epoxybutanes, 3-chloro-1,2-epoxypropane and the like. In this connection, phosphoric acid, phosphorous acid, the polyphosphoric acids, such as tripolyphosphoric acid, the polyraetaphosphoric acids, and the like.

The polyols used can have a hydroxyl number which can vary within a wide range. In general, the hydroxyl groups of the polyols used according to the invention are within the range of about 20 and below to about 1000 and above, preferably from about 25 to about 600 and especially from about 30 to about 450. The Ilydroxyl number is defined as that Number of mg of potassium hydroxide required for complete hydrolysis of the fully acetylated derivative made from 1 g of polyol is required. The hydroxyl number can also be defined by the following equation:

_O jj _ 56.1 χ 1000 χ f MG

where mean:

OH is the hydroxyl number of the polyol

f the functionality, d. H. the average

Number of hydroxyl groups per molecule of polyol, and

MW · the molecular weight of the polyol.

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Which polyol is used in each case depends on the end use of the polyurethane product to be produced from it. The molecular weight or the hydroxyl number is selected in a suitable manner so that flexible, semi-flexible or rigid foams or elastomers are obtained if the polymer produced from the polyol / Polyol mass is converted into a polyurethane foam. The polyols preferably have a hydroxyl number of about 200 to about 1000

^b (hard)
when used in rigid formulations, they have a hydroxyl number of from about 50 to about 150 for semi-flexible foams and from about 40 to about 70 or more when used in flexible foam formulations. However, the present invention is in no way restricted by these limits, but they merely serve to explain the large number of possible combinations of the above polyol coreactants.

The polyols preferably have viscosities from 100 to 2000 centipoise (cP) at 25 ⁰ C, while it is the ethylene and / or Propylenoxydaddukte of dihydroxyalkanes or Trihydroxyalka- NEN. The polyols should preferably be free of such groups / which catalyze the internal cyclization of polyacrylonitrile or polymethacrylonitrile (as stated above) and / or the decomposition of the catalysts * These groups are usually basic groups (e.g. amino groups ) »

The selection of styrene as a comonomer of choice with acrylonitrile or methacrylonitrile was made because of its economy, ease of access and relative ease Reactivity with acrylonitrile. This is because styrene is cheap, readily available in high purity and forms with acrylonitrile Polymerization azeotrope. The polymerization azeotrope of styrene and acrylonitrile is important because it ensures the production of a copolymer having a uniform composition. Furthermore, when selecting the comonomer, the glass transition temperature

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temperature (Tg) of the expected copolymer must be taken into account. The glass transition temperature of the copolymer in the polymer / l'olyol must be higher than the application temperature of the foam produced therefrom in order to give it good load-bearing properties. The Tg of an acrylonitrile / styrene (50/50 wt -%) -Mischpolymerisats is about 108 ⁰ C. The selection of methacrylonitrile as a comonomer of choice with styrene or α-methylstyrene based on its reduced tendency to discoloration (relative to acrylonitrile) and its favorable copolymerization kinetics with styrene and α-methylstyrene. Methacrylonitrile also has a high homopolymer glass transition temperature (Tg> 100 C). The choice of α-methylstyrene as the comonomer of choice with acrylonitrile or methacrylonitrile is based on its relative reactivity with acrylonitrile or methacrylonitrile, its high homopolymer glass transition temperature and its economic efficiency. It also forms a polymerization azeotrope with both methacrylonitrile and acrylonitrile.

Regarding the relative amounts of polyols and monomers used in the inventive Verfahrön holds that The reaction mixture contains: (1) 10 to 30 parts by weight of a Monomennischung I of (a) SO to 75 wt ⁰ "acrylonitrile or methacrylonitrile and (b ) 25 to 50% by weight of styrene or ^ (- methylstyrene, the weight percentages of the acrylonitrile and the styrene or α-methyl styrene being based on the total weight of these materials, and (2) 70 to 90% by weight of one normally liquid polyol, the percentages by weight of the monomer mixture and the polyol being based on the total weight of the monomer and the polyol Boosting is imparted as desired and if more than 30% by weight of the monomer mixture is used in the reaction mixture, the resulting polymer / polyol viscosity is higher than desired If less than 50% by weight of acyl nitrile are used in the monomer mixture, this becomes the result

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polyurethane foam produced a smaller improvement in load-bearing capacity vsrliehen as desired and the polymer / polyol ^ viscosity is higher than desired, and if more than 75 percent by weight of the acrylonitrile are used in the monomer mixture produced polyurethane foam with a low density (a formulation with a high water content) has a greater discoloration or Scorch as desired

The catalysts suitable for producing the polymer / polyol compositions according to the invention are known per se, free radical-generating PC catalysts of the vinyl polymerization type, for example peroxides, such as hydrogen peroxide, dibenzoyl peroxide, acetyl peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide, di-t -butyl peroxide, lauroyl peroxide, butyryl peroxide and the like; Azo compounds such as azobisisobutyroiiitrile and the like; Peroxy compounds, such as persulfates, perborates, persuccinic acid, diisopropyl peroxydicarbonate, and the like _"0 The polymerization can also be carried out in the presence of an inert organic solvent. Examples of solvents that can be used are toluene, benzene, acetonitrile, ethyl acetate, hexane, heptane, dicyclohexaiij, dioxin, acetone, Ν, Ν-dimethylformamide, N, N-dimethylacetamide and the like, including those known to be used as solvents are suitable for the polymerization of vinyl monomers. The only condition in the selection of the solvent and the polyol is that they must not interfere with the polymerization reaction of the monomer. If an inert solvent is used, it will generally be removed from the reaction mixture in a conventional manner before the polymer / polyol is used to make polyurethane foams.

In the case of the preparation of the polymer / polyol compositions according to the invention applied temperature is any temperature

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door at which the half-life of the catalyst is no more than 6 minutes (preferably not more than 1.5 to 2 minutes). The half-lives of the catalysts become shorter as the temperature rises. The maximum temperature used is not very critical, but it should be below the temperature at which considerable decomposition of the reactants oda * of the product occurs. The half-lives of these catalysts are known properties of the materials and they are known per se Methods measured. The half-lives are usually measured while the catalyst is in a solvent is dissolved, which practically does not react with the catalyst and does not decompose it. Examples of such solvents are liquid ones Colil hydrocarbons and liquid halogenated hydrocarbons. Reactive liquids, e.g. B. liquid amines are not suitable Solvent.

The temperature at which the half-lives of typical catalysts 6 minutes is the following:

Catalyst temperature ( ⁰ C).

Azobisisobiityronitrile Lauroyl peroxide De c an oy Ip er oxy d Benzoylpcroxyd p-Chlorobenzoy peroxide t-Huty1-peroxyisobutyrate Acctyl peroxide. Propionyl peroxide 2,4-dichlorobenzoyl peroxide t-butyl peroxypivalate

100 00 1 00 1 15th 1 15th 1 15th 1 05 1 102 95 95

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- ι · ι -

In the process according to the invention, the monomers are polymerized in the polyol. As a rule, the monomers are soluble in the polyol. It has been found that if the monomers are first dissolved in a smaller proportion of the polyol and the solution thus formed is added to the remainder of the polyol at the reaction temperature, this facilitates the mixing of the monomers into the polyol and clogs the reactor If the monomers are not soluble in the polyols, known methods (e.g., dissolving the insoluble monomers in another solvent) can be used to disperse the monomers in the polyol prior to polymerization. The conversion of the monomers into polymers which is achieved by the process according to the invention is remarkably high (for example, degrees of conversion of at least 95 % of the monomers are generally achieved).

While not wishing to be bound by any particular theory, it is believed that the initial yellowing of the commercially available Polymer / polyols made from acrylonitrile or acrylonitrile / methyl methacrylate mixtures are derived, and the discoloration or scorching of the foams made from them both on the inner Cyclization of the polyacrylonitrile contained therein to a "mesh-like" or "ladder-like" polymer go back, the has a chromophoric conjugated polyimine structure. A sequence length of this chromophore is more than 3 recurring Units are known to absorb visible light; H. discoloration occurs. It is believed that the structure of the Chromophore is the following:

Polyacrylonitrile

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"mesh-like polymer"

BATH ORIGINAL

It is known that by the introduction of a non-cyclisierendcn monomers in the polymer chain in the correct frequency \ prevents the formation of long sequence profiles of the chromophoric cyclized polyacrylonitriles ar the can.

The polymer / polyol viscosity is a complex function of the content of polymeric material, the initial polyol viscosity, the polymerization temperature and in this case the copolymer composition. While it is assumed that the first two parameters are determined by the Haganmacker equation, is the effect of the polymerization temperature and the mixed polycrystate composition not so easy to understand. It is believed that the effect of the temperature and the copolymer composition include the type and degree of grafting affected by changing these two sensitive parameters will. It is also known that by changing the polymer composition the copolymer density and the particle polarity are influenced, which is known to drastically affect the dispersion viscosity changes. Earlier attempts (cf. Canadian Patent 785 835) to produce a styrene / acrylonitrile (50/50 wt. I) copolymer / polyol using azobisisobutyronitrile as a catalyst suffered from clogging of the reactor (Formation of pebble-sized (gravel-sized) particles), whereby polymer / polyols were obtained, the foams with poorer quality physical properties (in particular with regard to the scorching of the foams produced therefrom) as desired. This known method was carried out under conditions which are essentially those in the method according to the invention conditions applied were equivalent, with the exception of the fact that the polymerization temperatures in the known process were below the temperature used according to the invention, when azobisisobutyronitrile was used as the catalyst with the same reactants. It is believed that the known process

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BATH ORIGINAL

Ren was disturbed by a relatively low monomer polymerization rate, which allowed the unreacted monomers to be incorporated into the already formed polymer particles (to be dissolved therein). ' This "plastifizierton" polymer particles are subject to shearing action, .which an agglomeration process provides that the ^M pebble "formation or results in extreme cases, clogging of the reactor. In the known method the reactor temperature is about was 97.5 ⁰ C, the half-life of According to a preferred embodiment of the invention (reaction at 115-120 ° C.) azobisisobutyronitrile has a half-life of 1.5 to 1.0 minutes obtained as by the inventive process (85 to ^90? s compared to more than 95%). This difference in relation to the conversion of the cause of the considerable differences in the particulate nature of the polymer / polyols prepared by the known process appears in comparison to the to be polymer / polyols produced by the process according to the invention. Known methods give compositions containing relatively large granules (e.g. those having a diameter greater than 0.254 cm (0.1 inch)) which precipitated out of the liquid phase of the polymer / polyol, while compositions according to the invention are obtained that contain relatively small particles (e. B. those with a diameter of less than 1 micron) that remain suspended in the liquid phase of the polymer / polyol. The compositions according to the invention are therefore suspensions which contain a liquid phase of unreacted polyol with small particles of homopolymer and / or copolymers of nitrile and styrene monomers suspended therein. The compositions also contain various polyol monomer graft polymers with various polymer contents. This Pf rop Για j -schpol / mer Iisatartcn with a low Polymergchalt (einciii high Polynigchalt) iiegui in .lot liquid phase of the suspension, while the types, with a high polymer content also sw pendlor te FeStSt (U ¹ I; dar ·. ; te hay.

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BATH ORIGINAL

It is known that when the polymerization temperature is increased (eg from 95 to 115 ^° C.) the reactivity ratio values of acrylonitrile and styrene or for any two different monomers become more equivalent to each other. Since this is the FAIL, higher polymerization temperatures appear to be a more "random copolymer ^tt and thus better foam properties are achieved with regard to the stability of the

Foam against scorching.

*) (random copolymer)

The process according to the invention gives polymer / polyol compositions with properties which are clearly different from the polymer / polyol compositions obtained from the same starting materials at lower temperatures. The polymer / polyol compositions according to the invention are therefore new compositions. In view of the prior art, and ά: τ complex nature of the structure-property-Bezichungen in obca discussed masses, it is difficult, the new Hate invention based on their exact chemical structure to fully characterize. Therefore, the compositions of the invention are best described in terms of the relative amounts and types of polyols and monomers used in their preparation and in terms of their most exceptional property, ie their ability to impart anti-scorching properties to polyurethane foam (ie foams with a substantially uniform white cross-section). Moreover, it concerns with the novel polymer / polyol compositions are white or cream liquids with relatively low viscosities (eg viscosities from 1000 to 2500, preferably 1000 to 1500 cP at '25 ⁰ C) _1, further include those prepared from these compositions Polyurethane foams with a low density (ie the foams with densities of less than 0.028 g / cm ³ (1.75 lbs / ft. ³ )) very good elongations (US to ITO "" are required according to ASTM DI 564-69 -Process), tear strengths (from 1.76 to 2.46 kg / cm ² (2.50-3.50 psi),

3 u 9 811/1 rn

BATH ORIGINAL

measured by the ASTM D1564 »69 method and 90% - permanent Deformations (from 3.0 to 15, measured using the ASTM U1564-69 method) on.

The invention also relates to a method for producing a polyurethane foam, in which one reacts and foams with one another: (a) a polymer / polyol composition according to the invention, (b) a organic polyisocyanate, (c) a catalyst for the reaction of (a) and (b) to form the polyurethane, (d) a blowing agent and (e) a foam stabilizer. The reaction and foaming can be carried out in any suitable manner, preferably using the one-shot method.

The organic polyisocyanates suitable for the production of polyurethane foams according to the invention are organic compounds which contain at least two isocyanate groups. Such verb are indungen known in the art of preparing polyurethane foams per se. Examples of suitable organic polyisocyanates are the hydrocarbon diisocyanates (e.g. the alkylene diisocyanates and the arylene diisocyanates) and known triisocyanates. Examples of suitable polyisocyanates are:

1,2-diisocyanate ethane, 1,3-diisocyanate propane, 1,2-diisocyanate propane, 1,4-diisocyanate butane, 1,5-diisocyanate pentane, 1,6-diisocyanate hexane, BisC3-isocyanatopropyl) ether, bisCS-isocyanatpropyl sulfide, 1,7-diisocyanatheptane, 1, S-diisocyanate-Z, 2-dimethylpentane, 1,6-diisocyanate-3-methoxyhexane, 1,8-diisocyanatoctane ,. 1,5-diisocyanate-2,2,4-trimethylpentane, 1,9-diisocyanatnonane, the 1,10-diisocyanatopropyl ether of 1,4-butylene glycol, 1,11-diisocyanatundecane, 1,12-diisocyanatododecane, Bis (isocyanathexyl) sulfide, 1,4-diisocyanatobenzene, 2,4-Diisocyanattöluol, 2,6-Diisocyanattoluol, 1,3-Diisocyanat-oxylene, 1,3-biisocyanate-ni-xylene, 1,3-diisocyanate-p-xylene, 2,4-diisocyanate-1-chlorobenzene, 2,4-diisocyanate-1-nitrobenzene and 2,5-diisocyanate-1-nitrobenzene as well as mixtures thereof.

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BATH ORIGINAL

In the case of the production of polyurethane foams according to the invention Process usable catalysts are

(A) tertiary amines, such as bis (dimethylaminoethyl) ether, trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, Ν, Ν-dimethylbenzylamine, Ν, Ν-dimethylethanolamine, N, N, N ', N ¹ -ctramethyl-1 , 3-butanediamine, triethanolamine, 1,4-diazabicyclo- / 2.2.27octane, pyridine oxide and the like;

(b) tertiary phosphines such as trialkylphosphines, dialkylbenzylphosphines and the like;

(c) strong bases such as alkali and alkaline earth metal hydroxides, alkylates and phenates;

(d) acidic metal salts of strong acids, such as iron (III) chloride, tin (IV) chloride, tin (II) chloride, antimony trichloride, bismuth nitrate and chloride and the like;

(e) chelates of various metals, e.g. B. those from acetylacetone, cenzoylacetone, trifluoroacetylacetone, ethylacetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetone imine, bis-acetylacetonealkylene diimines, salicyIaldehyde imine and the like. With various metals such as Be, Mg, Zn, Cd, Pb., Ti , Sn, As, Bi, Cr, Mo, Mn, Fe, Co, Ni or ions such as MoCL, UO ₂ and the like., Can be obtained;

(f) Alcoholates and phenates of various metals, such as Ti (OR) ₄ , Sn (OR) ₄ , Sn (OR) ₂ , Al (OR) ₃ and the like, in which R is alkyl or aryl, and the reaction products of alcoholates with carboxylic acids, β-diketones and 2- (N, N-dialkylamino) alkanols, such as the known chelates of titanium, which are obtained by equivalent processes;

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BATH ORIGINAL

-, .-- 2UZA7B

(g) Salts of organic acids with various metals, such as • alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni and Cu, such as. Example, sodium acetate, potassium laurate, Calciumhexanoat, tin (II) acetate, tin (II) octoate, tin (II) oleate, lead octoate, metallic driers, such as cobalt naphthenate and Mangnesium _s, etc .; and

(h) organometallic derivatives of tetravalent tin, trivalentcm and pentavalenters As, Sb and Bi, and metal carbonyls of Iron and cobalt.

Organotin compounds that are particularly worth mentioning include the dialkyltin salts of carboxylic acids, such as. B. dibutyltin diacetate, Dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, Dioctyltin diacetate, dibutyltin bis (4 ~ methylaminobenzoate) Dibutyltin ~ bis (6-methylaminocaproate) and the like. It can also Trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkylate or dialkyltin dichloride are used. Examples of such compounds are trimethyl tin hydroxide, tributyl tin hydroxide, triocty tin hydroxide, Dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin bis (isopropoxide), dibutyltin bis (2-dimethylaminopentoxide), Dibutyltin dichloride, Diocty! Tin dichloride and the like.

The tertiary amines can be used as primary catalysts for acceleration the reaction between the reactive hydrogen and the isocyanate or as secondary catalysts in combination with a or more of the abovementioned metal catalysts can be used. Metal catalysts or combinations of metal catalysts can also be used as accelerators without the use of amines. The catalysts are used in small quantities, for example from sth-ιΟ, ΟΟΙ to about 5%, based on that Weight of reaction mixture, used.

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BATH ORIGINAL

The foaming is achieved by using a small amount of a polyurethane blowing agent (foaming agent), such as water, in the reaction mixture (for example about 0.5 to about 5% by weight of water, based on the total weight of the polymer / polyol -Mass) or by using blowing agents that are vaporized by the exothermic reaction, or by a combination of these two methods. Examples of suitable polyurethane blowing agents are halogenated hydrocarbons, such as trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluomethane, dichloromethane, trichloromethane, 1,1-dichloro-1-fluoroethane, 1,1,2-trichloro-1,2,2-trifluoroethane, illo-cyclo-butane , Octafluorocyclobutane, and the like. Another class of propellants are the thermally unstable compounds that release gases when heated, such as e.g. 13. NjN'-Üinicthyl-NjN'-dinitrosotercph ^ halamid. The generally preferred foaming method in the manufacture of flexible foams is to use water or a combination of water and a fluorocarbon propellant such as B. trichloromonofluoromethane used. The amount of blowing agent (foaming agent) used varies depending on various factors such as e.g. B. the desired density of the foamed product. The anti-scoring properties of the polymer / polyol compositions are evident when at least some of the blowing agent is water, and the water is used in an amount that results in a foam having a density of less than 0.028 g / cm ³ (1.75 lbs / ft. ³ ) leads. In general, the use of water in an amount of at least 3.0% by weight, based on the total weight of the polymer / polyol composition, leads to a

3 3

Foam with a density less than 0.028 g / cm (1 _t 75 lbs / ft.)

According to the invention, it is also possible to use small amounts, for example approximately 0.001 to 5.0 wt. B. a "Pluronic" - or a "hydrolyzable" polysiloxane-polyoxyalkylene block copolymer, such as. As the block copolymers described in U.S. Patents 2,834,748 and 2,917,480,

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BAD ORlGlNAt

2247476

to use. Another suitable class of emulsifiers are the "non-hydrolyzable" polysiloxane-polyoxyalkylene block copolymers, e.g. B. the ί ^ ββΐ US Patent 3,505,377, in the. U.S. Patent Application No. > and block copolymers described in British Patent 1,220,471. The last-mentioned class of copolymers differs from the above-mentioned polysiloxane-polyoxyalkylene block copolymers in that the polysiloxane radical is bonded to the polyoxyalkylene radical via direct carbon-silicon bonds instead of carbon-oxygen-silicon bonds. These various polysiloxane-polyoxyalkylene block copolymers preferably contain 5 to 50 Cevi _t - ^? o Polysiloxane polymer, the remainder being polyoxyalkylene polymer.

The polyurethane foams produced according to the invention can have can be used in all areas in which foams made from conventional polymer / polyols are used and they are suitable particularly suitable for armrests, impact pads and mattresses *

The following examples are intended to explain the invention in more detail, without however, limit them to /.

Definitions

The names, symbols, Expressions and abbreviations have the meanings given below:

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Polyol I.

Polyol II polyol III

Made from polypropylene oxide and glycerine Polypropylenoxydtriol with a molecular weight of about 3000.

A polyalkylene oxide triol made from propylene and ethylene oxides and glycerine and having a molecular weight of about 3700; the alkylene oxide units are primarily in the form of blocks and the primary OH content is about 57.51; the ethylene oxide is used to terminate ( ^ca P) the triol. Based on its alkylene oxide content, the triol contains 90% by weight of C ₃ II ₆ O and 10 _{% by weight of SC 2} H ₄ O.

A polyalkylene oxide triol made from propylene and ethylene oxides and glycerine and having a molecular weight of about 4900; the alkylene oxide units are primarily in the form of blocks and the primary OH content is about 75%; the ethylene oxide is used to cap off the triol; Based on its alkylene oxide content, this triol contains 85 wt. IC ₃ IJ ^ O and 15 wt. IC ₂ II ₄ O,

Polyol IV

A polyalkylene oxide triol made from propylene and ethylene oxides and glycerin and having a molecular weight of about 4650; the alkylene oxide units are primarily in. the form of blocks before and the primary OH content is about 2.5 * »} besogen on its Alkylenoxydgehalt contains this triol 86 weight _f -SC ₃ Il ₆ O and 14 wt," * · C ₂ H ₄ Q,

3 0 9 811/112 3

Polymer / polyol Λ polymer / polyol B Polymer / polyol C.

Polymer / Polyol D Surfactant I.

Surfactant II A through polymerization of 20% by weight Acrylonitrile in 10% by weight of polyol I produced made commercially available polymer / polyol.

A through polymerization of 20 wt Styrene in 80% by weight of polyol I. Polymer / polyol

One by polymerizing 10% by weight of acrylonitrile and 10% by weight of methyl methacrylate Commercially available polymer / polyol produced in 80% by weight of polyol I.

One produced by polymerizing 20% by weight of acrylonitrile in 80% by weight of polyol III Polymer / polyol.

MeSi / IOSiMe ₂ ) _{6s 2 24 1 8 36 14} in which Mo "is methyl and Bu is butyl.

A mixture of 55% by weight

(CII ₃ ) ₃ Si0-

CH-

I ^a
-Si-O
■ I
CH ₇

ClI,

I ^Λ

bSi-Od

jj Si (CH ₃ ) ₃

72 C ₃ H ₆ O (C ₂ II ₄ O) ₂₀ (C ₃ II ₆ O) ₂₉ QI ₃

and 45% by weight of a mixture of C ₄ II ₉ O (C ₂ II ₄ O) ₁₈ (C ₃ II ₆ O) _{13 7} II (90% by weight) and

Wt .-%)

11/1 1.2.1

BAD OTUGtNAI.

Surfactant III

CH.

ι ·

₃ sio / si-o7 _5O -

CH,

Parts
'• Ionol "
3CF '
stripped

VCN
cP

CH

3.

.r -Si -Ο

C ₂ H ₄ C ₆ H ₅

CH.

-Si-O

Si (CH ₃ )

wherein R to 90 mol-5 Cllj-groups and

to 10 MoI-I?

C-CH-T groups means

A mixture of 80 wt .- $ 2,4-tolylene diisocyanate and 20% by weight of 2,6-tolylene diisocyanate.

Parts by weight

2,6-di-tert-butyl-4-methylphenol Tris (ß-chloroethyi) phosphate

The volatiles are removed by heating under reduced pressure.

Acrylonitrile

Centipoise at 25 ° C using a # 3 spindle on a Brookfield Viscometer at 100 rpm.

9 811/112 3

BATH ORIGINAL

Test procedure -

In the examples described below, the following test procedures were used:

test

"Indentation Load Deflection" ("ILD") Permanent deformation

tensile strenght

strain

Tear resistance

"Sac Factor" (stress value) Moisture aging, stress loss

Springback.

"CLD" = bending under pressure I "return" value

Evaluation of the foam color (scorching)

^1! Abbreviated Pill "(simplified" Pill "procedure)

»Cover No. 1 = 3" ---

procedure

according to ASTM D1564-69

ti

It

ti

ti

ti

ti

Il

tr

ti

ti

Il

Il

it.

ti

018 1171123 Scale: 0-80 units 0 = colorless; 80 = dark brown visual rating

ASTM D-2859-70 T modified (abbreviated) by using one test sample instead of 8 test samples in the Flame spread caused by an ignited Methenajnine pill out-> was called, recommended motor driving stuff, safety standard

BATH ORIGINAL

porosity

Line 1.27 cm (0.5 inch) thick foam sample is between two flanged plastic pipes with a diameter compressed by 5.7 2 cm (2 1/4 inches) to amines; this arrangement will then a component in an airflow system; air enters at one end of the pipeline at a controlled rate, flows through the foam sample and exits through a constriction at the lower end of the assembly; the pressure drop along the foam through the obstructed air passage is closed by means of an inclined Manometer measured; one end of the pressure gauge is on the upstream side of the foam and the other end is connected to the undercurrent kitc; the airflow on the upstream side is adjusted so that a pressure difference across the sample of 0.254 cm (0.1 inch) of water is maintained; the air porosity of the foam is in units of air flow per unit area of the sample in cubic feet per minute per square foot specified.

example 1

321 g of polyol I were placed in a 1 liter three-necked flask equipped with an addition funnel, a stirrer and a reflux condenser. The polyol was heated with a Ciasmantel with simultaneous passage of oxygen-free nitrogen at 110 ⁰ C. After nitrogen had been passed through for 15 to 20 minutes, the following mixture was continuously introduced into the flask over a period of 2 hours: 159 g of polyol I, 60 g of acrylonitrile, 60 g of styrene and 3.0 g of azobisisobutyronitrile. The temperature of the reaction mixture thus formed was kept at 110 ° C. during the polymerization. Less than 10 minutes after the start of the introduction of the mixture, the reaction mixture became cloudy as a result of small, apparently insoluble particles and

309811/112 3

BATH ORIGINAL

Upon polymerization, the reaction mixture became opaque to white suspended solids (less than 1 micron in diameter). No large particles (granules) were formed. After completion of the Monoraerzugabe the reaction mixture was heated an additional 30 minutes at 110 ⁰ C and then cooled and then released by stripping the unreacted monomers. The unreacted monomer was stripped for 4 hours absolute pressure on a rotary evaporator at about 10O ⁰ C and less than 10 mm mercury. The unreacted monomers were collected in dry ice traps. The conversion of the monomers to the polymer, based on the unreacted monomers collected in the dry ice, was more than 96.0%. The stripped, white polymer / polyol so formed had a Brookfield viscosity of 3072 cSt (Gentistokes) (spindle no. 2, 100 rpm at 25 ⁰ C).

Example 2

Example 1 was repeated, this time using 6 times the amount of starting materials and applying a reaction temperature of 115 ° C. The polymer / polyol so formed had a viscosity of 2100 cP (Gentipoise) at 25 ⁰ C and is hereinafter referred to as "polymer / polyol I".

Example 3

From the Polyrcer / Polyol I (the one described in Example 2 Procedure), flexible polyurethane foams were produced • with a low density and compared to other parts such foams were made from polymer / polyol A (a commercially available polymer / Polyol). Iis became the following foam formulation applied:

30981 1/1123

BATH ORIGINAL

2742A76

Polymer / polyol 100 parts 3500 g

Water 4.0 parts 140 g

Surfactant I 1.0 part 35 g

Bis (dimethylaminoethyl) ether 0.07 parts 2.45 g

Tin (II) octoate 0.35 parts 12.25 g

TDI 107 index 1710.0 g

The foam formulations were converted into polyurethane foams by the following procedure:

The surfactant, polymer / polyol, and TDI were weighed into an 8 liter stainless steel beaker fitted with a baffle and operated at 2000 rpm for 60 seconds with two 2.5 inch (6.35 cm) -6-blade turbine stirrers ( spaced 6.35 cm (2.5 inches) from the base of the shaft). After 15 seconds degassing was stopped, mixing was continued for 5 seconds, then the water / amine catalyst mixture was added, mixed for an additional 5 seconds, then stannous octoate was added and mixed for 5 seconds. The foam was poured into a paper-lined box of 61.0 cm by 61.0 cm by 50.8 cm (24 by 24 by 20 inches). The rise time of the foam was recorded. It was then left to harden overnight at room temperature. Scorch disks (5.08 cm (2 inches) thick) were removed from the horizontal center of the foam cake. The other foam physical properties were measured using a 6 inch sample taken from the bottom of the top half of the foam cake. The "scorch" rating was performed using a "Scorch ^tl disk sample from the center. The following physical properties of the foams were determined.

309811/1123

BATH ORIGINAL

Table I.

¹¹ Return "value,% Foam T Foam 2 improvement
of the show 2
opposite to
Foam 1 in% Polymer / poly oil Load ratio
(65 ILD / 25 ILD) A '" I. Foam rise time • 7
Foam density in g / cm
(lbs / ft. ³ ) 'WHERE sec. 78 sec. S ch aiuiip orosity
(ft, ³ / min./£t ^x . ² ) Permanent deformation,
90% 45.0 20.9 "ILD" in kg (lbs) 25% Tensile strength in kg / cm 27.9 (61.4) 31.5 (69.5) 13.2 65% Strain, % 52.0 (114.6) 54.4 (120) 4.7 25% Tear strength in kg / cm
(lbs / inch) 15.0 (33.0) 17.8 (39.3) 19.1 Scorch foam paint 53.8 56.6 1.87 1.73 0.0234 (1.46) 0.023 (1.43) 78.7 16.1 79 5
(reduced) 1.33 (18.8) 1.58 (22.5) 19.7 103 114 10.8 0.38 (2.12) 0.51 (2.85) 34.4 dark Ib raun cream colored

Example 4 "

Using 80 Cew.-I polyol I and 20% by weight acrylonitrile or a mixture of acrylonitrile and styrene, a number of polymer / polyols were made. The reaction temperature was 115 C. The other reaction conditions were the same as in Example 1. In the following Table HA are the properties of the resulting polymer / polyols.

309811/1123

BATH ORIGINAL

. 23-22-7-76

Table IIA

Weight 0,
V Styrene colour product ität, cSt Polymer / polyol CII ₉ = CHCN ' 13.40 ii / eiss Viscous 200 D ⁺ 6.60 11.74 White 35 650 E ⁺ 8.26 11.74 White 19th 200 F ⁺ 8.26 0.00 yellow 19th 450 G ⁺ 20.00 10.00 White 9 370 II 10.00 10.00 White 2 080 III 10.00 . 7.95 White 2 440 IV 12.05 6.00 cream 1 440 V 14.00 colors 1

no polymer / polyols according to the invention.

The data reported in Table IIA above show that lower viscosities and, compared to the polymer / polyol G, the improved color of the polymer / polyols according to the invention. the Data in Table IIA further illustrate that there is a certain minimum viscosity which is a function of the composition of the copolymer. A graphical representation of this data would provide an optimum viscosity for an acrylonitrile / The styrene ratio at etiva is 12.5 / 7.5, but acrylonitrile / styrene ratios down to 9/11 are sufficient low viscosities obtained.

The polymerization temperature used in the polymerizations given in Table IIA above was 115 ^° C. and was selected as a result of a brief study of the relationship between the polymer / polyol viscosity and the polymerization temperatures. The results of this investigation are in

309811/1123

BATH ORIGINAL

-.29 -

given in Table HB below. This relationship can be represented in the form of a diagram showing a turning point of Viscous itäts -temperature curve at 115 ⁰ C. Therefore 115 ^° C. was selected as the standard polymerization temperature for the other examples. The mixed polymer / polyol composition in the temperature study was polyol I / styrene / acrylonitrile (80/10/10 weight ratio).

Table HC

Temperature, C Viscosity, cP 100 8 280 110 3 072 115 .2 080 • 115 2,368 120 2 100 Example 5

From the polymer / polyol I and for comparison from your polyol I, the Polymer / Polyol A and Polymer / Polyol B, flexible polyurethane foams with a low density were made. It was the following foam formulations used:

cr ^ i, τ -I ^ foam

(Cew file) ■

Polyal I 100

P.oiymer / polyol A 100

Polymer / polyol I 100

Polymer / polyol B

water

Tin (I I) octoate

Bis (dimethylaminoethyl) ether

Surfactant I
TI) I (index)

4.0. 4.0 1 00 4.0 0.35 0.35 4th , 0 0.325 0.10 0.10 0 , 30 0.10 1.0
105 1.0
105 0 , 10 1.0
3098 1 1 j ° 1 ⁵ 12 3 1
1 , 0
05

BATH ORIGINAL

The foam formulations were made according to that described in Example 3 Process transferred to polyurethane stalls. The properties of the foams were as follows:

Table III

/ Min / ft. ² ) 25 * in kg / cm foam 1 2 3 4th Properties, in *) 65% 32.8 48.3 34.5 58.7 Porosity (ft. ³ 25% 45 36 34 37 Springback
(Ball rebound 20.2 (44.5) 27.2 (60) 28.1 (62) 16.9 (37.3) ILD in kg (lbs) 35.6
(78.8) 49.4
(108.7) 51.2
(113.5) 27.3
(60.2) 13.5
(29.8) 15.2
(33.4) 15.4
(34.0) 7.5
(16.4) Permanent set, $ 90 67.0 55.7 54.8 44.0 251 ILD return Tensile strength in kg / cm ^
(psi) 1.77 1.81 1.83 1.61 Sac factor Elongation in % 0.023
(1.44) 0.0232
(1.45) 0.0229
(1.43) 0.0254
(1.59) TI
Density p in g / cm
(lbs / ft. - ⁵ ) Tear resistance
(lbs / inch) 3.63 70.2 23.4 10.2 1.08
(15.4) 1.44
(20.5) 1.40
(19.9) 1.00
(14.2) 159 127 141 148 0.386
(2.17) 0.408
(2.29) 0.447
(2.51) 0.318
(1.79)

Moisture aging, Loss of stress

N / A

Evaluation of the foam color 0

N / A

70

23.4

16.7

309811/1123

BATH ORIGINAL

2242A

A comparison of the physical foam properties with the base polyol I (foam 1) with the properties of foam 4 (styrene polymer / polyol) shows that, surprisingly, by replacing 50% by weight ^? i acrylonitrile by styrene in the polymer contained in the polymer / polyol of the foam 3 not only the physical foam properties of the 100 ^? The above polyacrylonitrile polymer / polyol (Foam 2) was not adversely affected, but that an improvement was actually achieved in some of these properties. With regard to foam 4, these changes, with the exception of the percentage elongation, were not to be expected.

Example 6

From the polymer / polyols II, IV and V and for comparison from the Polymer / polyols A, F and D (see. The above "Definitions" and the above example 4 with regard to the composition of the polymer / Polyols), flexible polyurethane foams with a low Density made. The following foam formulations were used applied:

Parts by weight

Polymer / polyol 100 water 4.0

Bis (dimethylaminoethyl) ether 0.10

Tin (II) octoate 0.375

Surfactant II 1.0

TDI. 107 index

The foam formulations were made according to that described in Example 3 Process converted into polyurethane foams. The properties of the foams obtained were as follows:

3 0 9 8 1 1/1 '1? 3

BATH ORIGINAL

Table IV

co

CD CO

co

Polymer / Polyo1

Polyol I / VCN / styrene
(Weight ratio)

Rise time, sec.
Porosity, ft. ³ / min / ft ²
CLD in kg (lbs) (b) 251

651

251

Return value, I.

Load ratio

Density in g / cm " ⁵
(lbs / ft.3)

Permanent deformation,
90S

Tensile strength (b)
in kg / cn ^z (psi)

Elongation, % (b)

Tear strength in
kg / cm (lbs / inch)

CLD loss in %

A.
80/20/0

66
45

5.75 (12.7)

10.7 (23.5)

3.13 (6.9)

53.8 1.87

0.0234 (1.46)

73.7

1.36 (19.3)

107

0.58 8 (2.18)

Ii / A

V.
80/14/6

69

3.8 (a)

6.8 (15.0)

10.2 (22.6)

4.17 (9.2)

61.3 1.49 (a)

0.0214 (1.34)

84.5

1.72 (24.4)

153

0.495 (2.78)

25.3

IV 80 / 12.05 / 7.95

72

4.0 (a)

7.16 (15.8)

11 (24.3)

4.4 (2.7)

61.5 1.53 (a)

0.0224 (1.40).

27.8

1.61 (22.9)

147

0.445 (2.50)

27.7

II
80/10/10

74
21.4

6.16
(13.6)

10.3
(22.8)

3.79
(S, 35)

59.2
1.67

0.0234
(1.46)

55.8

1.41
(20.1)

0.47
(2.64)

22.7

F D

80 / 8.27 / 11.74 80 / 6.67 / 13.33

68
29.2

5.75 (8.28)

8.2 '(18.1)

2.34 (5.14)

61,7 2,1S

0.0234 (1.46)

79.1

1.25 (17.7)

142

0.48 (2.71)

21.9

68 36.5

2.87 (6.33)

6.4 (141)

1.82 (4.02)

63.4 2.23

0.022.4 (1.40)

79.6

0.86 (12.2)

119

0.377 (2.12)

25.9

it)

N>

(J)

To table IY

(a) Foams with a very low porosity often yielded unusual exposure values c. That is, the 25% CLD value increased, and as a result, the exercise ratio value often became lower than normal, fourth for the permanent Deformation tended to be high »

(b) All parameters responsive to density were "normalized" to a value for density of 0.024 g / cm ³

(1.50 lbs / ft. ³ ).

This data was calculated to be 0.024 g / cm (lbs / ft. 1.50) "normalized" to precisely determine the trends in foam properties. "Normalized" means a conversion the physical properties responsive to the density (i.e. the CLD, tensile strength, elongation and tear strength) to a usual density, in this case by dividing the property data by the following factor:

experimental foam density 1.50

It should be noted that then, the interpolymer composition fell considerably below 50% by weight acrylonitrile, the foam properties, such as e.g. B. bending under pressure (compression load deflection), tensile strength and the elongation in percent, decreased quickly. These approvals ran parallel to the rapid increase in polyol viscosity, as in the above Table HA given. The foam data show that with the polymer / polyol II prepared according to the invention, physical. Properties were achieved which were superior to those of the commercially available polymer / polyol A.

309811/1123

BATH ORIGINAL

Example 7

This example illustrates the continuous implementation of the method according to the invention using proportionally large amounts of raw materials in two stages. The first stage was in a standard Pfaudier autoclave performed while the second stage in a Marco Eeactor (e.g. a Marco Flomaster beactor model no. 2x290-294, the mode of operation of which is shown in example 1 of the Canadian patent 785 835 is generally described). The following materials were used in this manufacture:

Poly oil I

Hydroxyl number "52.51

pH 6.2

Alkalinity 0.000071

Color, Pt-Co 25

Water, % 0.066

Acrylonitrile

Water content, % 0.3

Color, Pt-Co 5

suspended material -

Refractive Index 1.3894

Inhibition level, ppm 37

Styrene

spec. Weight, 20/20 ⁰ C 0.9078

Acid -

Purity, wt% 99.7

Color, Pt-Co 10

Aldehydes, wt% 0.005

Sulfur, ppm 1

Refractive index 1.5475

3098 11/1123

.a.zobisisobutyronitrile; the commercial product "" VAZO "was used. '"

An inventive polymer / ^ oly.ol was produced by feeding a mixture of 79.311% of Polyol I, 10,344% of acrylonitrile, 10,344% styrene and 0.491% of azobisisobutyronitrile in a held to 115 +2 ⁰ C, provided with a stirrer 19 1 (5 gallons ) Autoclaves. The "feed rate" was 41.7 + 1 kg (92 + 2 lbs.) Per hour. The partially polymerized products of the autoclave were passed through the 11.4 l (3 gallon) Marco reactor maintained at 115 ° G. Marco reactor product was then transferred to 55 gallon drums, and the unreacted monomer was stripped from the latter product in a 300 gallon 1140 gallon reactor equipped with a stirrer intermittent sampling (at intervals of 30 minutes) from the reaction product of the Marco reactor, once this was in a state of equilibrium (e.g. after about 30 minutes of operation), showed that the white polymer / polyol had a uniform brook flow. Id viscosity of 10 050 + 50 cP (spindle # 3 at 26 ° C.) Inspection of the autoclave and Marco reactor after 25 hours of continuous polymerization showed little or no polymer deposit residue ymere was more than 95%. The polymer / polyol according to the invention produced in this way is hereinafter referred to as "polymer / polyol VI".

The following formulations were used to produce Polyurethane foams the polymer / polyols A, G and VI used.

98 11 / 11.2 3

ORIGINAL INSPECTED

476

component

■ polyol

water

Bis (dimethylaminoethyl) ether tin (II) octoate

Surfactant II

Men ge (parts by weight) 100 4.0 0.1 1.0 * variable Index

* the concentration varied to produce stable foams as given in Example 8 below.

As indicated in Example 3, the formulations were converted into polyurethane foams. The properties of the polymer / The polyols and the foams were as follows:

Polymer / polyol A

Polymer / polyol color yellow

Hydroxyl number 44.9

Brookfield viscosity, 23 ° C * 2580 cP

Concentration range of the

Tin (II) octoats (parts by weight) ** 0.275-

Scorch rating 65-70

cream colored

4-3.5 cP

25-0.375 0 ^ 425

25th

YI knows 43.4 1200 cP

0.25-0.375

<5

"Viscosity after removal of the unreacted monomers ** above this concentration the cells were closed ■. and below this concentration the foam ruptured in use of the above formulations.

It is well known that during the transition of a polymer / rolyolprozesses of the laboratory reactor (eg, a 1- or 2-1 pistons) via a pilot plant unit in ejne großtechnisehe product ionseinheit a gradual reduction dei ¹ Produktv.i s-

BATH ORIGINAL

viscosity occurs regardless of the type of product being made Polymer / polyol product. A comparison of the viscosities of the products of Examples 1 and 7 shows the same effect in the transition from small to large scale.

Example 8

With the polymer / polyol VI (the one according to the invention Procedure prepared as described in Example 7 above), flame tests were carried out. With these Tests it was about the doubled pill test, the Test Docket Mr. 3-3 and the ASTM D-1692 test. The results are given below.

2 pounds of foams tested were made according to that in the example above 3 prepared using the formulations given below:

component Weight point Polyol 100 water 3 3 Off as stated Surfakb ant 1.0 Bis (dimethylaminoethyl) ether 0.1 Tin (II) octoate * TDI 105 index

* for the production of stable foams the concentration

• varies as follows: while keeping the other formulation components constant the tin (II) octoate concentration was varied until the tin (II) octoate concentration was determined, which resulted in a crack-free, "open" foam.

In the following Table V the results of a simplified Pill tests (the samples were not preconditioned

/ HW

and only one sample was tested). In this test, a methenamine pill is placed in the center of a sample 8 inches diameter is ignited and the unburned distance is measured. The numbers in the The following table shows the unburned distances. The pill test is considered passed if this distance 2.54 cm (1 inch) or larger. A value of 0 shows that the sample was consumed (burned) in the test. The following table shows that in this test the polymer / Polyol VI foams containing surfactant II as a surfactant were the least flammable. When replacing of surfactant II through surfactant II in the formulations, the polymer / polyol VI foams were even better, compared to however, they were only better on the tape than the polyol I foams.

VI Table V 3CF content 20 parts 0 7.6 cm
(3 in.) 7.6 cm
(3 in.) C. 10 parts unburned distance 0 7.3 cm
(2-7 / 8 in.) 7.3 cm
(2-7 / 8 in A. simplified pill test 6.2 cm 8.25 cm
(2-3 / 8 in.) (3-1 / 4 in.) 8.1 cm
(3-3 / 16 in.) 7.6 cm
(3 in.) Polyol Surfactant II 0 Surfakbant III 8.9 cm
(3-1 / 2in. 0 7.95 cm 7.95 cm
(3-1 / 8 in.) (3-1 / 8 in.) VI 5 parts 0 0 8.55 cm
(3-3 / 8 in. Polymer / polyol C. 0 7.95 cm
(3-1 / 8 in. Polymer / polyol A. 8.25 cm
(3-1 / 4 in. Polymer / polyol Polyol I. Polymer / polyol Polymer / polyo1 Polymer / polyol

Polyol I 6.2 cm 7.95 cm 7.95 cm

(2-3 / 8 in.) (3-1 / 8 in.) (3-1 / 8 in.)

30981 1/1123

2242 ^ 76

The next test that these foams were given in order to evaluate them, wax dea? so-called "Docket 2Ee". 3-3 "-35est (Ifetional Highway Safety Bureau, Department of Transportation Motor Tehicle Safety Standards). The" criterion for passing this test is that the burn resistance for two horizontal foam samples is less than four inches ( 4 inches) per minute. The results obtained are recorded in Table TI below. In the Surfactant JI range, the polymer / polyol A-seams were openly the most easily flammable foams. At 5 parts of 3CS ¹ , the polymer / polyol C foam had the lowest slurry rate, but only one sample of the polymer / polyol foam at 10 parts of 3CF was self-extinguishing and the other had a burn rate of 4.59 cm (1.81 inches ) per IELnirbe, while both Polyol I samples were self-extinguishing. In the Surfak ™ tant III series, the polymer / polyol Tl foams were slightly better than the polyol I foams. ■

Table TI Docket ITr. 3-3 test

Surfactant II

Polyol - TI 5 parts 3CF content 20 parts S.E. ^ S.E. S. E. S.E, - C. 10 parts average burning speed
speed in cm (inches) / minute (1.21) ' S.E. S.E. S.E. A. 4.6
(1.81) 4,6, SE
(1.81) S.E. 3.58rS..E.
(1.41) 9.05 »SE
(3.57) Polymer / polyol (i%) S.E. B.E. .S.E. Polymer / Polyo1 5.85.
(2.30) Surfactant IH Polymer / polyol TI 5.24
(2.06) S.E " Polyol I. C. S.E. A. -S.E ,. Polymer / polyο1 Polymer / Polyo1 Polym er / Polyo1 BATH ORIGINAL Polyol I.

Footnotes to Table VI

(a) S.E. means self-extinction and indicates that the Sample burned less than 3 »8 cm (1.5 inches);

(b) Both samples were tested, only one being self-triggering and the other was more than 1.5 inches (3.8 cm) burned.

The ASTM-D-1692 test was then carried out. In this Trap were tested 5 samples and each had to be extinguished, before it burned 5 inches. This test is in the Regcil than that of the three described in this example Tests considered most difficult test. In the following Table VII are the burning rate, the burning distance and the rating specified for this foam series. Table VII shows that the polymer / polyo] Α foams are the most easily flammable Foams and that the polymer / polyol C foams were more flammable than the polymer / polyol VI and polyol I foams.

Polypropylene

Polymer / polyol VI
Polymer / polyol C.
Polymer / polyol A
Polyol I.

Table V II ASTM D-1692 Test

Surfactant II 3CF content

5 parts
valuation

Parts

Speed in cm (inches; / minute

20 parts

Distance in cm / inches)

^B > ⁸ J '« (3.19)

1.12.7 (5)

B 7.9, 12.7 (3.12X55

B. 8.9, 12.7 (3.50) (5)

B 7.5 * 12.7 (2.95) (5)

S.E 6.85, 5.1 (2.69) (2.0)

B 7.3 12.7 (2.88) (5)

B 7.0. 12.7 (2.753 (

SE ·, 5.7. 5.85 _λ (2.24) (2.3)

SE, 6.4 (2.5D

S.E., 5,65,5,35 (2.23) (2.1)

B, 5.5, 7/12 (2.17) (5)

S.B ·. 4.83 (1.90)

3 0 9 8 11/112

Portetzun ^ of Table VII

Surfactant III

Polymer / Polyol VI SE, 8,8,4,57) SE, 7.1, 3.56 ₅ SE 51 2.3

(3.46) (1.8) (2.80) (1.4) (2.0O) (0.9)

Polymer / Polyol 0 S.E. x 8.45, 6.1 / 3rdE., 7.15.4.3, S.E., 5.8, 3.8

(3.33X2.4) (2.81) (1.7) (2.28) (1.5)

Polymer / Polyol A B. 8.74, 12.7 S.E ,, 5.4, 5.76, S.E. 4.65, 9.8

(3.44) (5) (2.13) (2.27) (1.83) (3.85)

Polyol I SE ₀ , 5.96 5.7, SE, 4.2, 3.48, SE, 4.5, 1.02

(2.35) (2.25) (1.65) 0.37) - (1.773 (0.4)

(a) B means "burns"
Example 9

The polymer / polyols shown in Table VIII below were converted to polyurethane foams using the general procedure described in Example 3 above and using the formulations shown in Table IX below. The properties of the foams are given in Table X below. The foam properties show that all of the inventive polymer / polyols (the polymer / polyols VI, VII, VIII and IX) which had been produced from various polyol starting materials (polyols I, II, III and IV) produced good foams. ■ ■

30981 1/1123

Tabel VIII Polymer/
Polyol Molecular weight
of the initial
Polyol viscosity
CcP) A. 3,000 2,000 D. 4 950 3 800 IV 3,000 1,400 VII (2) 3 700 1,200 VIII (3) 3 740 1,200 IX (4) 4 950 2,200

Settlement (weight ratios)

Polyol I / VCN (80/20) Polyol III / VCN (80/20) Polyol I / VCN / Styro1 (80/10 /

Polyol IV / styrene / VGN (80/10/10)

Polyol II / styrene / VCN (80/10/10)

Polyol III / VCN / styrene (80/10/10)

(1) VGN means acrylonitrile

(2) Prepared according to the general procedure used in Example 2 Procedure using the starting materials given in this table

(3) Prepared according to the general procedure applied in Example 2 using those given in this table Raw materials

(4) produced according to the general procedure used in Example 2 using the methods given in this table.

- the same starting material.

Table IX '

Foam shape amount (parts by weight)

mottled 1 2 3 4 5 6

Polymer / poly oil

A 100

IV 100

VII

VIII

D 100

IX 100

H ₂ O 4.0 4.0 4.0 4.0 4.0 4.0

3 0 9 8 11/1

Continuation of! Table IX

Bis (dimethyCLamino-

ethyl) ether 0.10 0.10 0.075 0.05 0.03 0.03

Tin (ll) octoate. 0.30 0.35 0.275 0.30 0.175 0.175
Surfactant I 1.0-1.0 1.0 1.0 1.0 1.0

TDI, index 105 105 I05 IO5 105 107

Table X

J foam properties

Foam** . 12 3 4-

Scorch competition

management (scorch rating

tion (1) 65 5 5 5 - -

Porosity, ft. /

min / ft. ^ ^ 34.5 51.2 24 32 29.2

Springback, ball rebound in% 32 35 35 35 2. ¹ ? 30th

ILD kg (lbs) 25 % * 27.7. 29.5 '27.3, 28.7, 29.5, 31.4

(61.0) (65.0) (60.2) (63.2) (65.1) (69.2)

65 % 51.5 54.0 44.0 51.0 56.6 62.0

(113.2) (119, O) (97, O) (112.0) (124.5X136.0)

25 % (return) ¹ 5.6 16.2 15.0 16.05 14.7 16.5

return; ₍ ^ j ₄₎ ^^ ^ _Q) ^ ₃ J ₍₃₂ j ₃₎ ^^

Eeturn value in% 56.5 54.8 54.8 55.5 49.6 52.6 Load ratio 1.86 1.83 1.61 1.77 1.91 1.96

Density in g / cmr

(lbs / ft.3) 0.0244-0.023 0.0234 0.0248 0.0265 0.0271

(1.52) (1.43) (1.46) (1.55) (1.65) (1.69)

permanent deformation,

90 % compression,

Height loss, % 36.7 23.4 7.84 9 * 35 66.7 35.5

Tensile strength in

kg / cm ^d (psi) * 1.35 1.46 1.39 1.60 1.27 1.19

(18.7X20.8) (19.8) (22.7) (18.0) (16.9)

Elongation, % * 120 148 I7I 148 123 93

Ice resistance in

kg / cm (lbs / inch) * O _# 3? 7 0.47 0.515 0.512 0.6 0.53

(2 _t 11) (2.63) (2.88) (2.87) (3.37) (2.96)

Loss of stress

after 5 hours 19 * 2 23.4 23.5 18 * 7 H / A N / A

moist storage

3 0981 t / 1fi; 23 ^ _;

Footnotes to Table X

* The data responsive to density changes, "normalized"

• to 0.024 g / cm ⁵ (1.50 lbs / ft. ^)

** Foam made from the appropriately numbered foam

■ formulation

(1) Schaiim scorching rating: scale from 0 to 80, where 0 = white (no scorching) and 80 = dark brown
(severe scorching)

An important consideration in the preparation of the polymer / polyols of the invention is to improve conversion
of the volatile monomer into the non-volatile copolymer.
This improves the economy and the efficiency of the process. The conversions of the monomer into the
Polymers in the manufacture of the various polymer / polyol compositions described above were as follows:

Polymer / polyol Conversion of the monomer in% . I. > 96 II > 95 JII > 97 IV r ^ 98 V ^ 95 VI > 95 VII > 95 VIII > 95 IX N 95

The above % conversions were from the unreacted monomers recovered as described in Example 1
calculated.

Patent claims:

30981 1/1123

Claims (1)

Claims Μ J Process for the production of a liquid polymer / polyolefin characterized in that one (1) 10 to 30% by weight of a monomer mixture of (a) 50 to 7 ^> % by weight of acrylonitrile or methacrylonitrile and (b) 25 to 50% by weight of styrene or α-methylstyrene, the percentages by weight of the Acrylonitrile and styrene or α-methylstyrene by
are based on the total weight ± & materials, dissolved or dispersed ^v in (2) 70 to 90% by weight of a normally liquid polyol, the weight percentages of the monomer mixture and the polyol based on the total weight of the monomers and the polyol are related, polymerized in the presence of a free radical catalyst at a temperature at which the half-life of the Catalyst is not longer than 6 minutes, 2. The method according to claim 1, characterized in that azobisisobutyroiiitrile is used as the catalyst and that the temperature is at least 10O ⁰ O. 3. The method? According to claim 1, characterized in that the monomer mixture about 50 percent by weight acrylonitrile and about 50 percent Contains wt .-% styrene. 4 ·. Method according to claim 1, characterized in that about 20 wt .-% of the monomer mixture are polymerized, the is dissolved or dispersed in about 80% by weight of the polyol. '5 ·' Method according to Claim 1, characterized in that an alkylene oxide adduct of a polyhydroxyalkane is used as the polyol will. 309811/11 2.3 6. The method according to claim 1, characterized in that that such a temperature is used during the polymerization at which the half-life of the catalyst is no longer than 2 minutes. 7. The method according to claim 2, characterized in that the temperature is 115 to 120 ° C. 8. A process for the production of a polyurethane foam, characterized in that one reacts with one another and foams (A) a polymer / polyol composition according to claim 1, (b) an organic polyisocyanate, (c) a catalyst for the reaction of (a) and (b) to produce the polyurethane, (d) a blowing agent and (e) a foam stabilizer, 9. The method according to claim 8, characterized in that one makes a flexible foam ~ "~ and that the Implementation and foaming carried out according to the one-shot process that the polymer / polyol composition is an alkylene oxide adduct of a polyhydroxyalkane with a hydroxyl number of 40 to 70 and water as blowing agent, wherein the water is used in such an amount that a foam with a density of less than 0.028 g / cnr (1.75 lbs / ft.). 10. Flowable or liquid polymer / polyol mass, thereby characterized in that it can be converted into a polyurethane foam with a substantially uniform white cross-section is by reaction with water and an organic polyiso-cyanate and that it is the free radical generating catalyst catalyzed reaction product that is formed becomes 10 to 30% by weight in the polymerization of (1) Mixture of (a) 50 to 75% by weight of acrylonitrile or methacrylonitrile and (b) 25 to 50% by weight styrene or α-methylstyrene, 3098 11/1123 being the weight percentages of acrylonitrile and styrene or α-methyl styrene based on the total weight of the / materials are based, dissolved or dispersed in (2) 70 to 90% by weight a normally liquid polyol, the weight percentages of the blend and polyol being based on total weight of the monomers and the polyol. 11 .. polymer / polyol composition according to claim 10, characterized in that the conversion of the monomers into the polymer is at least 95 % » 12. Polymer / polyol composition according to claim 11, characterized in that that the monomer mixture is about 50% by weight of acrylonitrile and contains about 5% by weight styrene. de-attorney (Dr. V /. / Schmiea-Kowarzik 30 9 811/112 3 ORIGINAL INSPECTED