MXPA96006186A - Polymy cauchotoso de baja nebulosi - Google Patents

Abstract

There is a need for polymers that offer increased heat resistance, ultraviolet light resistance, and characteristic nebulosity sheets for use in automotive interiors. It is particularly critical for polymers that are used in making skin composites for automotive instrument and door panels to exhibit excellent heat resistance, ultraviolet light resistance and low haze characteristics. This invasion more specifically describes a rubbery polymer that can be mixed with polyvinyl chloride to make leather-like compositions having good resistance to heat and ultraviolet light, the rubbery polymer being comprised of repeating units that are comprised of (a) butyl acrylate, or optionally a mixture of butylacrylate and 2-ethylhexylacrylate containing up to about 40% of 2-ethylhexylacrylate, (b) at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methylacrylate, and ethylacrylate, (c) acrylonitrile, (d) styrene, (e) a surfactant selected from the group consisting of sulphonates and sulfate derivative, (f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylates, and (g) an agent of reticulation

Description

LOW NEBULOSITY CUTE POLYMER This is a continuation in part of Serial No. 08 / 440,032, filed on May 22, 1995, currently pending, which was a divisional of Serial No. 08 / 306,291, filed on September 15, 1994. , now issued as United States Patent 5,415,940, which was a divisional of Seventh Edition No. 08 / 043,076, filed on April 5, 1993, now issued as United States Patent 5,380,785.

BACKGROUND OF THE INVENTION Automotive instrument panels and door panels are typically composite that are made of a rigid reinforcement that supports a semi-rigid urethane foam with the semi-rigid urethane foam being covered with a skin composite. These leather compounds typically they are mixtures of p 1 ivinyl chloride (PVC) with a nitrile rubber (NBR). Nylon rubber is included in these mixtures as a permanent modifier for PVC that provides a high degree of flexibility The automotive industry is currently moving to more aerodynamic body designs than typically I nc I and in larger glass areas. These design changes have significantly increased the aging requirements for heat and ultraviolet light in automotive interiors. This, in turn, has increased ignif ically the demands imposed on pollinators that are used in automotive interior panels. Heat and light stabilizers can be used to improve the heat and ultraviolet light aging characteristics of conventional PVC / NBR blends that are used as automotive interior penis skins. However, the degree to which the aging characteristics of said mixtures can be improved by the addition of additives is limited. In fact, there is a demand for performance characteristics in such applications that has not been realized so far by the use of heat and light stabilizers. For example, it would be highly desirable that skins used in automotive panels resist discoloration and aggradation under conditions of high heat and intense ultraviolet light throughout the life of the pen. Improved haze behavior is also of great importance to the automotive industry. Nebulosity is caused by the condensation of volatile compounds that vaporize from the interior panel through the screen or windshield or side windows of the vehicle. The NBR / PVC blends offer a disposition of-physical properties that make them useful as a skin composition for automotive panels. The NBR acts as a permanent levibylation monomer for PVC. It also acts as a shrinkage control agent, and helps enhance and improve grain retention. The NBR in said mixtures also provides gauge control of vacuum formation and exhibits low nebulosity characteristics. The NBR is highly compatible with the -PVC and has the ability to recycle itself. It is essential for any polymer that is substituted by NBR to exhibit these characteristics; essential techniques.

SUMMARY OF THE INVENTION The present invention relates to a polymethyl methacrylate which can be mixed with PVC to make leather-like compositions. These compositions are particularly useful for manufacturing skins for automotive interior panels. The skin compositions that are made using this cauteryous polymer provide superior heat and ultraviolet light resistance than those made using conventional NBR / PVC blends. The rubbery polymers of this invention also offer low cloudiness, low odor, shrinkage and grain retention characteristics. They also act as an enhancement aid and as a modification of permanent lexibi lization. The rubbery polymers of this invention also have characteristics that make them useful in construction application. This invention more specifically describes a rubbery polymer? Ut5 can be mixed with polyvinyl chloride to make leather-like compositions that have good resistance to heat and ultraviolet light, the rubbery polymer being comprised of repeating units which are comprised of 9a) buty lacrylate, or optionally a mixture of butylated acrylate and 2-ethylhexylacrylate containing up to about 40% of 2-ethylhexylacrylate, (b) at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methacrylate and ethylacrylate, (c) acrylonitrile, (d) styrene (3) a surfactant selected from the group consisting of sulfonates and sulfate derivatives, 9f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylates, and (g) a crosslinking agent. The present invention discloses a process for preparing a rubbery polymer that can be mixed with polyvinyl chloride to make leather-like compositions having good resistance to heat and ultraviolet light, the process comprising the steps of (1) polymerizing (a) buty 1 acr i 1 ato, (b) at least one member selected from the group consisting of methylmet. Crylate, ethyl methacrylate, methylacrylate and ethanol, (c) acrylonitrile, (d) a crosslinking agent and (e) a surfactant agent selected from the group consisting of sulfonates and sulfate derivatives, and 9f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylase, under emulsion polymerization conditions to produce a latex containing seed polymer.; (2) add (a) styrene, 9b) additional acrylonitrile, and (c) crosslinking agent additional to the latex polymer containing latex under polymerization conditions pro emulsion resulting in the formation of an emulsion containing the rubber polymer.; and (3) recovering the rubbery polymer from the emulsion containing the rubbery polymer. The present invention further discloses a process for preparing a rubbery polymer that can be mixed with polyvinyl chloride to make leather-like compositions having good resistance to heat and ultraviolet light, the process involving the steps of (1) polymerizing ( a) buti lacr i lato, (b) at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate, (c) acrylonitrile, (d) ) a crosslinking agent, (e) an agent-surfactant selected from the group consisting of sulfonates and sulfate derivatives, and (f) a dispersant selected from the group consisting of condensation products of aromatic-formaldehyde and pol icarboxy 1 atos, under conditions of limiterization by emulsion to produce a latex containing seed polymer; (2) add (a) styrene, (b) additional acrylonitrile, and (c) crosslinking agent additional to the latex containing seed polymer under polymerization-by-emulsion conditions resulting in the formation of an emulsion that has the rubbery polymer; (3) adding an aminoalcohol to the emulsion containing the rubbery polymer; and (4) recovering the rubbery polymer from the emulsion containing the rubbery polymer.

The present invention also discloses a leather-like composition useful in automotive applications which is comprised of (1) polyvinyl chloride, (2) an astiflating agent, (3) a rubbery polymer that is comprised of repetitive units that are comprised of (a) buti lacri lato, or optionally a mixture of buti lacri lato and 2-ethi lhexi lacri lato containing up to about 40% of 2-ei lhex i 1 acr i 1 ato, (b) at least one selected member from the group consisting of methyl methacrylate, ethyl methacrylate, methylacrylate and ethylacrylate, (c) acrylonitrile, (d) styrene, (e) a surfactant -selected from the group consisting of sulfonates and sulfate wastes, (f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylates, and (g) a crosslinking agent. The present invention also discloses a panel for automotive applications which is comprised of a non-remirghtable urethane foam that is supported by a rigid reinforcement, in which the semi-rigid urethane foam is covered with a skin similar to leather that is comprised of ( 1) polyvinyl chloride, (2) an astifling catalyst, and (3) a rubbery polymer that is comprised of repeating units that are comprised of (a) butyl-acrylate or optionally a mixture of butylated acrylate. and 2-ethylhexyl acrylate containing up to about 40% of 2-ethylhexH acrylate, (t) at least one metal selected from the group consisting of methyl methacrylate, ethyl methacrylate, methylacrylate and ethyl alcohol, (c) acrylonitrile, (d) styrene, (e) a surfactant agent selected from the group consisting of sulphonates and sulfate derivatives, (f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylates, and (g) a crosslinking agent.

Detailed Description of the Invention The rubbery polymers of this invention are synthesized using an emulsion polymerization technique of free radionuclide. These rubbery polymers are comprised of repetitive substances which are derived from (a) butylactic acid, or optionally a mixture of buty lacrylate and 2-ethylhexyl-1-acrylate containing up to about 40%. % of 2-et i 1 hex i 1 acr i 1 ato, (b) metH methacrylate, ethyl methacrylate, methyl 1 acrylate, or eti 1 acrylate, (c) acrylonitrile, (d) styrene, ( e) a surface active agent selected from the group consisting of sulfonates and sulfate derivatives, (f) a dispersant selected from the group consisting of - condensation products of aromatic formaldehyde and polycarboxylates, and (g) a reagent agent. iculation. The crosslinking agent is typically a multifunctional acrylate, a multi-functional methacrylate or divinylbenzene. Some specific examples of crosslinking agents that can be used include ethylene glycol methacrylate, divinylbenzene, and 1,4-butamide dimethacrylate.

Technically, the rubbery polymers of this invention contain repeating units (chain linkages) which are derived from (a) buty lacrylate, or optionally a mixture of butyl acrylate and 2-ethylhexyl lacrylate containing up to about 40% strength. 2-ethylhexyl ester, (b) methyl methacrylate, ethyl methacrylate methyl lacrylate, or ethyl ester, (c) acrylonitrile, (d) styrene, - (e) a surfactant selected from the group consisting of in sulfonates and sulfate derivatives, (f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylates, and (g) a crosslinking agent. These repeating units differ from the monomers from which they are derived in that they contain a carbon-to-carbon bond less than that present in the respective monomer. In other words, a carbon-to-carbon double bond is consumed during the polymerization of the monomer towards a repeating unit in the rubbery polymer. In this way, in that the rubbery polymer contains various monomers in effect it means that it contains repeating units which are derived from these monomers. The rubbery polymers of this invention will normally contain (1) from about 40 weight percent to about 80 weight percent butyl acrylate, or optionally a mixture of butyl acrylonitrile and 2-ethyl alcohol. hex i 1 acrylate containing up to about 40 weight percent of 2-et ihex i 1 ac i 1 ato, (b of about 5 weight percent of about 35 per cent by weight of methyl methacrylate) 1 ato, ethyl methacrylate, methylacrylate or ethyl alcohol, (c) from about 4 weight percent to about 30 weight percent acrylonitrile, (d) from about 3 weight percent to about 25 weight percent. percent-weight styrene, (e) from about 0.1 weight percent to about 6 weight percent of a surfactant is selected from the group consisting of sulphonates and sulfate derivatives, (f) of about 0.1 weight percent to about 6 weight percent of a selected dispersant from the group consisting of condensation products of aromatic aldehyde and polyhydric carboxy, and (g) from about 0.05 weight percent to about 8 weight percent of a crosslinking agent. These rubbery polymers will preferably contain - (a) from about 50 weight percent to about 80 weight percent butyl alcohol, or optionally a mixture of butyl alcohol and 2-ethyl alcohol. containing up to about 40% of 2-ethylhexylacrylate, (b) from about 3 percent by weight to about 25 percent by weight of at least one member selected from the group consisting of methylmercury , ethyl methacrylate, meth i 1 acrylate and eti 1 acrylate, (c) from about 6 weight percent to about 30 weight percent acrylonitrile, (d) about 5 per cent by weight to about 18 weight percent styrene, (e) from about 0.3 weight percent to about 5 weight percent of a dispersant selected from the group consisting of aromatic formaldehyde condensation products and polycarboxylates, and (g) about 0.5 percent and n weight to about 4 weight percent of a crosslinking agent. The rubbery polymers of this invention are more preferably comprised of repeating units which are derived from (a) from about 55 weight percent to about -75 weight percent butyl lactitol, or optionally a mixture of butyl alcohol and 2-ethylhexate lactide containing up to about 40% 2-ethylhexyl 1-acrylate, (b) from about 5 weight percent to about 20 weight percent of at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methylene acrylate and ethyl ester, (c) from about 10 weight percent to about 25 weight percent acrylonitrile, d) from about 8 percent by weight to about 14 percent by weight of styrene, (e) from about 0.5 weight percent to about 4 weight percent of a surfactant selected from the group consisting of in sulphonates and sulphate derivatives, (f) of around 0 .5 weight percent to about 4 percent in weight of a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and po 1 i -carboxylates, and (g) of about 1 percent by weight to about 3 weight percent of a removal agent.

The percentages reported in this paragraph are based on the total weight of the rubbery polymer. The rubbery polymers of the present invention are synthesized in an aqueous reaction mixture using a free radical polymerization technique. The reaction mixture used in this polymerization is comprised of water, the appropriate monomers, an appropriate free radical initiator, a crosslinking agent, a surfactant selected from the group consisting of sulfonates and sulfate derivatives, and a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylates. The reaction mixture used in this polymerization technique will normally contain from about 10 weight percent to about 80 weight percent of monomers, based on the total weight of the reaction mixture. The reaction mixture preferably will contain from about 20 weight percent to about 70 weight percent of monomers and more preferably from about 40 weight percent to about 50 weight percent monomers. The reaction mixtures used in carrying out these polymerizations will typically contain from about 0.1 phm (parts per hundred parts of monomer by weight) to about 5 phm from at least one member selected from the group because it consists of methallic salts. of alkyl sulfates and alkyl salts of alkylsulfonates, and from about 0.1 phm to approx. 5 phm of at least one dispersant selected from the group that you cosmed in condensation products of aromatic dehyde and polycarboxylates. It is generally preferred that the reaction mixture contain from about 0.25 phm to about 4.25 phm of the metal salt of the alkylsulfonate the metal salt of the alkylsulfate and from about 0.25 phm to about 4.25 phm of the dispersant selected from the group - which consists of condensation products of aromatic formaldehyde and polycarboxylates. It is usually more preferred that the reaction mixture contain from about 0.4 phm to about 3.5 phm of the metal salt of the alkylsulfonate or the metal salt of the alkylsulfate and from about 0.4 to about 3.5 ph of the dispersant selected from the group consists of condensation products of aromatic formaldehyde and polycarboxylates. The free radical polymerization technique used in this synthesis is usually initiated by including a free radical initiator in the reaction mixture. Virtually any type of compound capable of generating free radicals can be used as the free radical initiator. The free radi cal generator is normally employed at a concentration within the range of about 0.01 phm to about 1 phm. Commonly used free radical initiators include the various peroxygen compounds such as potassium persulfate ammonium persulfate, benzoyl peroxide, di-t-butyl peroxide hydroperoxide, dicumyl peroxide, peroxide 2, - d coorobenzoyl, decanoyl peroxide, lauryl peroxide, eumeno hydroperoxide, p-menthane hydroperoxide, t-butyl hydroperoxide, acetyl peroxide, methyl peroxide, succinic peroxide, peroxy dicypyl idicarbonate, peroxyacetyl t-butyl tart, t-butyl 1-peroximleic acid, t-butyl peroxybenzoate, t-butyl peroxymethyl acid, t-butyl peroxybenzoate, perxodium, aceric lecithin, and its like; The various azo compounds, such as 2-t-butyl-1-azo-2-cyanopropane, dimethyl isobutyrate, azodium, butyl ether, 2-t-butyl-azo-1-cyanocyclohexane, 1-t. The present invention also relates to the following compounds: anionic lohexane and the like, the various alkyl percetals, such as 2,2-bis- (5-butyl-1-peroxy) butane, and the like. Water-soluble pro-genyl free radical initiators are especially useful The emulsion polymerizations of this invention are typically carried out at the temperature ranging from about 20 ° C and 88 ° C. At temperatures above about 889C, the monomers of the acrylate 1, such as butylated acrylate, have the tendency to boil. In this manner, a snap jacket would be required to heat said alkyl acrylate monomers to tratures in excess of about 88 ° C. On the other hand, at polymerization tratures of less than about 55 ° C, a reduction initiating system is required by operation to ensure satisfactory polymerization rates. The sulphonate and sulfate derivatives which are useful in this invention as surfactants are commercially available from a wide variety of sources For example, Du Pont sells Sodium Sulphate 1 under the MR brand Alkanor, Browning Chemical Corporation sells Sodium Dodecylben MR Sulphonates under the brand Urafyl Dl-85, and Ruetger-Nease Chemical Company sells Sodium Sodium Sulphate under the brand name. MR brand Naxonate Hydrotrope. Some examples represent. Other sulfonate surfactants that may be used include toluene-xi sodium lens sulfonate, sodium toluene sulfonate, sodium sulphonate sulphurates, sodium sulfoate sodium decolide, sodium dodecyl sodium benzene sulphonate, sulfite dodecyl sodium sulphonate. 1-sodium octane sulfonate, sodium tetradsulfonate, sodium pentadsulfonate, heptadsu sodium lonato and to luei. potassium sulfonate. The metal salts of alkylbisulfonates which are a highly preferred class of sulfonat surfactant The metal will usually be sodium or potassium with sodium being preferred. The sodium salts of alkylbisenulfonates have the structural formula: wherein R represents an alkyl group containing from 1 to about 20 carbon atoms. It is preferred that the alk group contains from about 8 to about 14 carbon atoms. The sulfonate surfactant can be a mixture of (ono) dialkyl ether disulfonates. The advantage of the disulfonate structure is that it contains two ionic charges - per molecule instead of one as is the case with conventional alkyl sulfate surfactants. Mixtures of (ono) diethyl ether derivatives which are useful in the practice of this invention are commercially available from a wide variety of sources. For example, Dow Chemical sells -Dowfax MR alkylated diphenyl oxides, disulfonates that are of the structural formula: S03Na S03Na wherein R is an alkyl group that is typically -CfiH13, -C10H? 1 ~ C12H25 '^ ~ C16H33"The mono- and didodecyl-1-oxide derivatives are sold by American Cyuanamid as DP0S-45 surfactants. suitable for use in this invention are available commercially available from Witco and Hoechst AG The sulfate surfactants which are useful in the practice of this invention include metal silanes of alkyl sulfates having the structural formula R0S0-X and salts Metallic alkylsulfates having the structural formula: R0 (CH2ch20) S03X, wherein X represents a metal group, such as sodium or potassium, sodium lauryl sulfate, ethanolamine-nalauri sodium sulfate and triethanolamine sulfate. they are representative examples of commercially available sulphate surfactants The dispersant used in the polymerizations of this inversion are usually formaldehyde condensation products. gone aromatic or pol icarboxi latos. The condensation products of aromatic formaldehyde are normally poly-its lyphonates which are the reaction product of aromatic and formaldehyde compounds. These soaps of aromatic formaldehyde condensation product can be made by a relatively simple process. For example, in said process, 200 parts of naphthalene are reacted with 200 parts of 98% sulfuric acid-for 5 hours at a temperature of about 1655. The solution then made is subsequently cooled and diluted with 90 parts of water. . Then, 107 parts of 30% formaldehyde solution are added and the mixture is stirred for 20 hours at a temperature of about 80 ° C. Towards the end of this reaction period, the mixture is gradually heated to 100 ° C. The neutralization is carried out subsequently at 20 ° C to 25 ° C with about 165 to 180 parts of 25% ammonia solution. The neutralization product is then filtered, if necessary, dried in a vacuum dryer.

Numerous variations of this synthesis are possible, and a wide range of aromatic compounds and their derivatives can be reacted with aldehydes, ketones and compounds that eliminate the aldehyde groups. For example, (a) dispersants produced by condensation of aromatic sulfonic acids and benzyl or benzoin cioride.; (b) dispersants produced by the condensation of various alkylsulfonic acids with a halogen-arylsulfonic acid; and (c) dispersants produced by densation of phenols sulfonates or 2-naphthols with formaldehyde and various nitroget compounds. . Some representative examples of aromatic formaldehyde end products are shown below: Production Constituents Structural Units Naphthalene + H SO »+ formaldehyde Naphthalene + cresol + H2S04 + formaldehyde I sopropi 1 benzene + H? S0. + formaldehyde H C-, CH-CH.

So3Na CH3S03Na Phenol + H2S04 formaldehyde The carboxylate is also a polymeric water-soluble dispersing agent. For example, methacrylic acid can be purified to provide a water-soluble homopolymer which can be used as a carboxylate dispersant. The copolymers of maleic acid, acrylic acid, maleic acid, maleic acid, ethyl vinyl ether and di isobutyl-maleic acid (DIBMA) are also very useful in the practice of this invention. Carboxylate dispersants are commercially available from a variety of sources. The free radical emulsion polymerization used in synthesizing the rubbery polymers of this invention is typically conducted at a temperature that is within the range of about 10 ° C to about 95 ° C. In most cases, the polymerization temperature used will vary between about 20 ° C and about 80 ° C. The polymerization is carried out in a two-step batch process. In the first step, a latex containing seed polymer is synthesized. This is done by polymerizing (a) butyl acrylate, or optionally a mixture of butyl acrylate and 2-ethylhexyl acrylate containing up to about 40% 2-ethylhexyl acrylate, (b) at least one selected member from the group consisting of methyl methacrylate, ethyl methacrylate, methylacrylate and ethyl ester, (c) acrylonitrile, and (d) a crosslinking agent. The latex containing seed polymer is typically prepared from a mixture of monomer containing from about 40 to about 90 weight percent butyl acrylate, or optionally a mixture of butylated acrylate. 2-ethylhexyl lactide containing up to about 40% 2-ethyl-1-hexylacrylate, from about 5 to about 35 weight percent of methyl methacrylate, ethyl methacrylate, methylacrylate, or ethyl acrylate, about 2 to about 30 weight percent of acrylonitrile, and about 0.25 weight percent to 6 weight percent of the crosslinking agent. Typically, for the monomer component used in the first step, it is preferred to include from about 50 weight percent to about 85 weight percent butyl acrylate, or optionally a mixture of butylacrylate and 2-ethyl alcohol. lacrylate containing up to about 40 of 2-ethylhexyl lacrylate, from about 5 weight percent to about 30 weight percent ethyl alcohol, ethyl methacrylate, methylacrylate or methyl methacrylate, from about 4 weight percent to about 28 weight percent acrylonitrile, and from about 0.5 weight percent to about 4 weight percent of the removing agent. It is generally more preferred that the monomer loading composition used in synthesizing the seed polymer latex contain 60 percent by weight of air to about 80 percent by weight of butyl acrylate, or optionally a metal. butylated 1 acrylate and 2-ethylhexyl 1 acrylate containing up to about 40% -2-ethyl-1-hexylacrylate, from about 5 weight percent to about 25 weight percent methyl. lmetacri lato, ethyl methacrylate, methylacri lato, or ethyl lactide, from about 5 weight percent to about 25 weight percent acrylonitrile, and from about 1 to about 3 percent by weight reticulation. After the seed polymer latex has been prepared, styrene monomer, additional acrylonitrile monomer, and additional crosslinking agent are added to the latex containing seed polymer. As a general rule, from about 4 parts by weight to about 30 parts by weight of e-silyne, from about 1 part by weight to about 20 parts by weight of additional acrylonitrile, and from about 0.01 to 2 parts by weight of the crosslinking agent is they will add In this second stage of the polymerization, it is preferred to add from about 6 parts by weight to about 22 parts by weight of the tyne, from about 3 parts by weight to about 12 parts by weight of acrylonitrile, and from about 0.05 parts by weight to 1 part by weight of the crosslinking agent. Typically, more than about 10 parts by weight to about 17 parts by weight of styrene is preferred, from about 4 parts by weight to about 8 parts by weight of acylonityl, and from about 0.1 parts by weight to about 0.5 parts. by weight of the crosslinking agent which are added to the semidry polymer latex to initiate the second phase of the polymerization. A wide variety of blocking agents can be used in carrying out the polymerizations of this invention. Some representative examples of crosslinking agents which can be used include difunctional acrylates, difunctional methacrylates, trifunctional acrylates, trifunctional methacrylates and divinylbenzene. The 1-butanediol-dimethacrylate has proven to be particularly useful as the crosslinking agent. In most cases, the polymerization will continue until a high monomer conversion has been achieved. After the polymerization has been completed, it is usually desirable to add an aminoalcohol to the emulsion to deodorize the latex. The aminoalcohol will usually be of the structural formula H0-A-NH? wherein A represents an alkylene group containing from 2 to about 20 carbon atoms. It is usually preferred that the amino alcohol contains from 2 to 10 carbon atoms with amino alcohols containing from 2 to about 5 carbon atoms being most preferred. Ethanolamin, (H0-CH2-CH2-NH2) which is also known as 2-aminoethanol and 2-hi-droxyethylamine is a representative example of a preferred aminoalcohol. Some additional examples of preferred amino alcohols include 3-aminopropanol, 4-aminobutanol, 2-amino-2-methyl-1,1-propanol, 2-amino-2-ethyl-1-, 3-propanediol, N-methyl- 2,2- -iminoethanol and 5-aminopentanol. This deodorization step will be carried out under conditions that allow the aminoalcohol to react with n-butylacrylate and residual acrylonitrile that is present in the emulsion. This reaction will continue through a wide range of temperature and the stage of the reaction. Deodorization can be conducted at any temperature that is within the range of about 59C to about 95eC However, due to practical reasons, the deodorization stage will normally be carried out at a temperature that is within the range of about 20SC at approximately 709C. Since the reaction is faster at higher temperatures, the amount of reaction time necessary will decrease with increasing temperature. For example, at a temperature of about 20 ° C, a residence time in the deodorization stage of one to three days may be required. On the other hand, at a temperature of about 65 ° C, only about two hours of reaction time are normally required. The amount of time required for the aminoalcohol to react with the residual n-buty lacrylate monomer and the residual acrylonitrile number will also depend on the level of amine-alcohol used. As a general rule, from about -0.05 weight percent to about 2 weight percent of the aminoalcohol will be added, based on the total weight of the emulsion. More typically from about 0.1 weight percent to -about 1.5 weight percent of the aminoalcohol will be added. It is usually preferred to use from about 0.3 weight percent to about 1 weight percent of the amino alcohol.

The rubbery polymer made by the two-step batch polymerization process is recovered from the -emulsion (latex) after the optional deodorization step. This can be achieved using conventional coagulation techniques. For example, coagulation can be achieved by adding salts, acids, or both to the latex. After the rubbery polymer recovers by coagulation, it can be washed to further reduce odors. This can be achieved by simply pouring or spraying water on the rubbery polymer. The rubbery polymer can also be lasered by placing it in a water bath that will additionally reduce the odor. After washing, the rubbery polymer usually dries. It is sometimes advantageous to convert the dry rubbery polymer to a powder for ease of use. In this case, it would be beneficial to add a dividing agent to the rubbery polymer. Some representative examples of cleaving agents that can be employed include calcium carbonate, polyvinyl chloride emulsion, and silica. Calcium carbonate is a highly desirable dyeing agent that can be used in such applications. The rubbery polymers of this invention can be mixed with polyvinyl chloride to make compositions similar to leather. These leather-like compositions offer an excellent combination of properties for use in making leather compounds for panels used in automotive applications. These leather-like compositions can be prepared by mixing the rubbery polymer into polyvinyl chloride (PVC) using conventional mixing techniques. It is highly preferred that the rubbery polymer be in powdered form when mixed into PVC to make such leather-like compositions. A wide variety of plasticizers can be used - which are compatible with polyvinyl chloride resins. Some representative examples of plasticizers that are highly suitable for this application include abietic derivatives, such as hydroabietiol alcohol, methyl abietate and hydrogenated methyl abietate; acetic acid derivatives, such as cumylphenyl acetate; adipic acid derivatives, such as benzyloctyl adipate, dibutyl adipate, diisobutyl adipate, di- (2-ethexyl 1) adipate, diisononyl adipate, diisooctyl adipate, dinonyl adipate . linear adipate of C7 «, -dicapril adipate, octyldecyl adipate (n-octyl adipate, n-decyl), straight chain alcohol adipate, di-decyl adipate (adipate di di sodeci lo), adipate of ibutoxieti lo, high molecular weight adipate, polypropylene adipate, adipate -of modified polypropylene; acelaic acid derivatives, such as diclohexyl acelate, di- (2-ethylhexyl) acelate, di-n-hexyl acelate, low temperature plasticizer, diisooctyl acelate; benzoic acid derivatives such as diethylene glycol dibenzoate, dipropylenglycol dibenzoate, diethylene glycol benzoate and di-propylene glycol benzoate mixture, proprietary low-stain, neopenti glycol dibenzoate, glyceryl tribenzoate, timeti loletane tribenzoate pentaerythritol tribenzoate, cumylphenyl benzoate; polyphenyl derivatives such as hydrogenated terphenyl; citric acid derivatives, such as triethyl citrate, tri-n-butyl citrate, acetyltriethyl acetate, acetyl tri-n-butyl isolate, acetal-tributyl citrate; epoxy derivatives such as butyl epoxy stearate, epoxy type plasticizer, epoxy-type asthmatic acid talat, alkyl epoxy stearate, epoxidized butyl ester, epoxidized -octyl talate, epoxidized soy bean oil, trig 1 epoxidized cellulose, expoxidized soy bean oil, epoxidized sol gyrol oil, epoxidized type plasticizer, epoxidized linseed oil, epoxidized talato ester, 2-et i 1 hexy 1-epoxy talate, octyl stearate epoxy; proprietary esters such as proprietary ester and mixed ester; ether derivatives, such as cumylphenyl benzyl ether; formal derivatives such as butyl carbitol formal; fu-atic acid derivatives, such as dibutyl fumarate, diisooctyl fumarate, dioctyl futerate, glutaric acid derivatives such as mixed dialkyl giutarate and dicu i Ifeni glutarate; Glj_col derivatives such as diethylene glycol di pei argonato, trieti lengiol di pei argonato, di- (2-eti lbutirato) of trieti lengl icol, di-caprj_ lato de t iet i lengl icol, di- (2-eti 1 trieti lengl icol hexoate, trieti lengl icica dicaprylate, tetraeti lengl icol dicaprylate, di - (2-ethe ltoxoate of polyethylene glycol, butyl glycolate pta 1 i -yl butyl, triglyceride of fatty acid oil vegetable, fatty acid triethyl ester, halogenated dibasic acid derivatives, such as mixed dibasic ester, petroleum derivatives, such as aromatic hydrocarbons, isobutyl-rich derivatives, such as di-butbutyrate, 2, -tr imeti 1 - 1, 3-pentandol, isophthalic acid derivatives such as di (2-et i 1 -hexyl) isophthalate, diisooctyl isophthalate, dioctyl-1-softa-1-ato, lauric acid derivatives, such as butylaurate , monolaurate of 1,2-pro-pyleneglycol, monoethyl ether laurate of eti lensl icol, ethylene glycol monobutyl ether laurate, glycerol monolaurate, polyethylene glycol-400- d 1 aurate; melitates such as n-octyl trime-litate, n-decyl, tr-octyll trimellitate 1-n-deci 1 or trimellitate of tr ii sononi, trimethylate of tii soocti lo, tricapryl trimellitate, diisoctyl trimellitate Monoisocyanate, triisodecyl trimellitate, tri (C7 alkyl) trimellitate, tri-2-ethexy1-hexylo trimellitate; nitrile derivatives such as fatty acid nitrile; oleic acid derivatives such as butyl butylate, 1,2-propylene glycol monooleate, ether ethylene glycol monobutyl ether oleate, tetrahydrofuranuryl oleate, glyceryl oleate monooleate; paraffin derivatives such as chlorinated paraffins, diethylene glycol diol, triethylene glycol dicarbonate, 2-butoxyethylglycate dihydrate; p astif inates phenoxy such as acet i 1 -paracu i lphenol; phosphoric acid derivatives such as tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresium phosphide phosphate, tricresyl phosphate, tri-isopropyl phosphate, phosphates of alkyl aryl, difeni phosphate 1-xi leni lo, phenyl isopropylphene-nyl phosphate; phthalic acid derivatives such as alkyl benzene phthalates, dimethyl phthalate, dibutyl phthalate, di-isobutyl phthalate, dihexyl phthalate, butyloctyl phthalate, butyl isodecyl phthalate, butyl iso-hexylate phthalate, cliiso phthalate nonyl, dioctyl phthalate, di- (2-ethexyl) phthalate, n-octyl 1-n-decyl phthalate, hexyl octyl deciio phthalate, didecyl phthalate diisodecyl phthalate, di iso iso phthalate io, diundecyl phthalate, butyl 1 -ethexyl phthalate, butylbenzyl phthalate, octyl 1 benzyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, alkylaryl phthalate and 2-ethylhexyl phthalate 1 isodecyl; ricinoleic acid derivatives such as metyllacetyl ricinoleate, n-butylacetyl ricinoleate, triacetyl glycolleate ricinoleate; sebacic acid derivatives such as dimethyl sebacate, dibutyl sebacate and dibutyl alcohol sebacate; stearic acid derivatives such as glyceryl tri-acetoxy stearate, butyl acetoxy stearate, methi pentachlorostearate and methoxylethyl acetoxy stearate; sucrose derivatives such as sucrose benzoate; sulfonic acid derivatives such as alkylsulphonic esters of phenyl; castor oil derivatives such as castor oil methyl ester and castor oil isooctyl ester; and terephthalic acid derivatives such as dioctyl reftalate. However, to obtain an IP skin of low nebulousness, the selected plasticizers must be subjected to nebulosity test before use to ensure that their use does not lead to cloudiness. These leather-like compositions typically contain from about 40 to 160 parts by weight of the rubbery polymer, from about 1C to about 50 parts of a plasticizer, and from about 0.1 to about 5 parts-by weight of an antidegradant per 100 parts. in weight of polyvinyl chloride. Typically it is preferred that these leather-like compositions contain from about 60 to about 120 parts by weight of the rubbery polymer, from about 15 to about 40 parts of the plasticizer, and from about 0.5 to 3 parts of an antidegradant (by 100 parts of PVC). It is more preferably preferred that the leather-like composition contain from about 70 to about 90 parts by weight of the rubbery polymer, from about 20 to about 30 parts by weight of the plasticizer, and from about 1 to 3 parts by weight. weight of the anti-degradant per 100 parts by weight of the PVC. These compositions will also generally contain an acrylonitrile-butadiene-styrene resin (ABS resin). The leather-like composition will typically contain from about 15 parts to about 80 parts of ABS resin per 10C parts of PVC. The leather-like composition preferably will contain from about 25 to about 55 parts by weight of the ABS resin per 100 parts by weight of the PVC. It is generally more preferred that the leather-like composition contain from about 30 to about 40 parts by weight of the ABS resin per 100 parts by weight of the PVC. Typically, various colorants and / or pigments will also be added to the composition to achieve a desired color. The leather-like compositions of this invention are useful in a wide variety of applications. For example, they have been found to be extremely valuable when used - to make skins for automotive panels. These panels are typically comprised of a semi-rigid urethane foam that is supported by a rigid reinforcement and covered by the leather-like composition of this invention. These skins are made by calendering the leather-like compositions of this invention and then cutting them to the desired size and configuration. These skins for automotive applications that are made with the leather-like compositions of this invention offer noticeable heat resistance, ultraviolet light stability and low cloudiness characteristics. These are highly desirable features that can help prevent the skin of automotive components from cracking during the nromai life of the vehicle. The rubbery polymers of this invention may also be mixed with other halogen-containing polymers (in addition to PVC), styrenic polymers (styrene-containing polymers such as acrylonitrile-styrene-acrylate (ASA), polyolefins, polymers). and polyamides to produce compositions that exhibit good resistance to heat and ultraviolet light.These polymeric compositions can be used in the manufacture of a wide variety of useful articles, such as profiles, mounds, inlays, floors, carpets, hoses, cables and footwear. Virtually -any type of polyamide (nylon) can be used when preparing these mixtures.These nylons are usually prepared by reacting diamines with dicarboxylic acids.The dicamines and dicarboxylic acids that are used when preparing these nylons will usually contain about from 2 to about 12 carbon atoms, however, the nylons that can be used in these mixtures they can also be prepared by addition polymerization. Some representative examples of nylons that can be used include nylon-6, 6, nylon-6, nylon-7, nylon-8, nylon-9, nylon-10, nylon-11, nylon-12, and nylon-612. These nylons will typically have an average molecular weight of number that is within the range of about 8,000 to about 40,000 and more will typically have an average molecular weight in number that is within the range of about 10,000 to about 25,000. Some representative examples of polyolefins that may be used include linear low-density polyethylene, high density polyethylene, polypropylene, polybutylene and modified polyolefins, such as poly (ethylene vinyl acetate) which is known as EVA. This invention is illustrated by the following examples which are for the purpose of illustration only and are not to be construed as limiting the scope of this invention or the manner in which it may be practiced. Unless specifically indicated otherwise, all parts and percentages are provided by weight.

Example 1 In this experiment, a rubbery polymer was made using the techniques of this invention. The polymerization is carried out in a reactor having a capacity of 100 liters. The reactor was equipped with an axial flow turbine agitator operated at 110 rpm (revolutions per minute). The reactor was charged with 74.6 kg (kilograms) of water, -0.92 kg. of a medium ester maleate soap (made with fatty alcohol of C ,, -), 0.31 kg. of a 50 percent aqueous solution-of potassium hydroxide, 0.062 kg of sodium dodecyl-1-benzene, 18.0 kg. of n-buti 1 acri 1 ato, 2.6 kg. of acrylonitrile, 5.1 kg. of meti 1 acr i 1 ato, 0.38 kg. of 1,4-butanediol di-methacrylate, 0.078 kg of t-dodec and 1-mercaptan, and 0.058 kg of potassium persulfate. A temperature of about 60 ° C was maintained through the polymerization. When a total solids content of 25 percent was achieved, 0.025 kg was added. of additional potassium persui-fato. This first polymerization step was carried out over a period of about 2 1/2 hours. This first stage polymerization resulted in the production of seed polymer latex which was used in the second stage of the polymerization. In the second stage of the polymerization, 1.47 kg. of acrylonitrile, 3.4 kg. of styrene, 9.C50 kg. of di vi n i 1 benzene, and 0.009 kg of t-dodecymercaptan were loaded into the cue reactor -contains the seed polymer latex. Polymerization continued until a solids content of approximately 30 percent was reached. The latex produced was white colored, had a pH of about 0.5, had a viscosity of 3 Srookfieid-approximately 6 centipoise iCPS, a surface-to-air tension of 49 dynes per centimeter and a particle size. Approximately 60 points. Without embarking, e. Latex IL 'J a concentration of acr i .onitr i lo residual to o? or cr.c-ni '' -_- 'J -3? p (pcTü-s or rilLóo),?, n? conn ation of nb "?, acti_r.o residual and air &dedcr of b2 ppm and had an odor were e .os v; - the cempô = ro cemôro residual of e ^ ine an medarie crom = ' e re f 1 a - eqas i e "Ce x hec a cc aou 1 or s ü L sec L'2p: emontc y $, _- - -c: < \ rd a sec sec cac Ce mine mine is the gas chromatography that contains 24 ppm of residual acrylonitrile and 300 ppm of n-buty lacrylate. The dry rubber had an undesirable odor. The rubbery polymer made was also tested for nebidity characteristics. In the method used, the condensate from a 10 gram sample held at 100 ° C was captured for 16 hours in a thin sheet of chilled aluminum that was supported on a glass plate. After the 16-hour period, it was determined gravitrically that it had formed -about 4 mg of condensate.

Example 2 In this experiment, a leather-like composition was made by mixing the rubbery polystyrene synthesized in Example 1 to PVC resin. This mixture was prepared by mixing 35 parts of ABS resin, 80 parts of the rubbery polymer, 25 parts of a plastiff, 1.5 parts of antidegradants, and 4.5 parts of a red dispersion stabilizer to 100 parts of the PVC resin. A Farrel plastic mill of 20.3 cms. heated with oil, operated at 1769C was used for the preparation of the compound. All powders, liquids and stabilizers were first mixed in a Hobart mixer to form a rough dry mix. The dry mix and the elastomer were banded in the mill and mixed for 15 minutes before laminating at free 0.040 +/- 5. The test was conducted on laminated sheet samples. The prepared leather-like composition was determined to have physical characteristics that make it highly suitable for use in making skin compounds for panels used for automotive applications. Tension resistance, elongation at break, 100% modulus and Shorea D hardness of the leather-like composition made are reported in Table I (Example 2). The leather composition was also evaluated to determine its stability to heat and ultraviolet light. The light aging studies were conducted in an accelerated weathering tester Q-U-V that was equipped with a UVB-313 lamp. A cycle of aging consisted of 6 hours of light and 4 hours of humidity of 100 percent at 659 C with repeated cycles -continuous to the total hours reported in Table I. The samples were 2.54 cms. x 7.62 cms. of size. The heat aging was conducted by the ASTM 573-78 air oven heat aging method, with ASTM C die samples. The tension properties are detern? They were prepared before and after aging with a United tension tester model FM30-DM1VA at 50.8 centimeters per minute crosshead speed, 6.35 cms. of separation of clamp and 2.54 cms. of banking brand.

Comparative Examples 3-4 In this experiment, conventional skin compounds were prepared for comparative purposes. In these experiments, the same procedure as described in Example 2 was employed, except for the fact that an ASA resin was replaced by the rubbery polymer used in Example 2. These reams of ASA were terpolymers of acrylonitrile, styrene and an acrylate monomer. In Comparison Example 3, the ASA MR resin used was ASA Mobay Baymod KU3-2069A resin with the MR-Baymod resin KU3-2079A being used in Comparison Example 4. The physical properties of these conventional COJI skin compounds and their characteristics of resistance to heat and light-violet are compared with those of the leather-like compositions in this invention in Table I.

Comparison Example 5 In this experiment, an additional skin compound was prepared using the same procedure as described in Example 2, except for the fact that a crosslinked nitrile rubber was replaced by the rubbery polyol used in the - example 2 and except for the fact that the amount of ABS resin used was increased to 60 parts. The physical properties of the conventional skin composite prepared in this experiment and its heat and ultraviolet light resistance characteristics are compared with those of the leather-like compositions of this invention in Table I.

Table I COMPOSED Ex. 2 Ex em. 3 Ex em. 4 Ex em. 5 Voltage, MPa 17.4 21. .7 22.8 20.2% Elongation 105 197 116 296 Module 100%, MPa 17.2 - 22.6 16.9 Shore Hardness A 60 67 70 62 Aged in an Air Oven at 1109C,% E Change 504 hours 0 -25.6 - 37 -20 1008 Hours -29 -23.9 -78 -67 1512 hours -28 -26.2 -80 -90 1992 hours -34 -52 -95 Aged in Air Oven at 1219C,% E Change 70 Hours 0 0 -71 -12 144 Hours -3 -9.4 -79 -10 288 Hours -15 -11 -76 -70 384 Hours - 20 -11.1 -75 -94 480 Hours -42 -35.8 -96 -82 528 Hours -44 -37.6 -98 -95 QUV 313 Color Change of Aging Pro Light 70 Hours 0.9 3.6 3.9 2..7 200 Hours 7.9 8.5 7.1 9.0 360 Hours 16.5 18.8 18.6 18.2 540 Hours 16.5 19.1 21.5 20.9 As can be seen by reviewing the data in Table I, the physical properties of the leather-like composition made with the rubbery polymer of this invention were very comparable to the conventional skin compounds shown in the Examples 3, 4 and 5 of Comparison. However, the leather composite made using the rubbery polymer of this invention had greatly improved heat aging characteristics after 1,992 hours at 110 ° C. Its resistance to heat 121 C - proved to be comparable with the heat stability exhibited in - Example 3 of Comparison However, the skin composite made using the rubbery polymer of this invention had greatly improved heat resistance at 1219C compared to the skin composite made in Comparison Example 4 and in Comparison Example 5. The leather-like composition made in Example 2 proved to be superior to both conventional skin compounds made in Comparison Examples 3, 4 and 5. In this manner, the skin compounds of this invention exhibit greater resistance to ultraviolet light than conventional skin compounds made with ASA resins.

Example 6 In this experiment a rubbery polymer was synthesized using a procedure similar to the procedure employed in Example 1. This polymerization was conducted in a reactor having a capacity of 100 liters. The reactor was equipped with an axially-flow turbine agitator operated at 110 rpm. The reactor was initially charged with 70.92 kg. of water, 0.87 kg - dodecanol monomaleate, 0.40 kg of a 50% aqueous solution - of potassium hydroxide, 0.06 kg. of sodium dodecyl benzene sulfonate, 0.06 kg of sodium pyrophosphate, 0.05 kg of triethanolamine, 22.13 kg of n-buti 1 acri 1 ato, 2.60 kg of acrylonitrile, 1.30 kg of methylmethacrylate, 0.65 kg of 1, 40 butandioldimetacrite, 0.08 kg of t-dodecymercaptan and 1.56 kg of a 5% solution of potassium persulfate. A temperature of about 35 C C was maintained through the polymerization. When a total solids content of approximately 24 percent was achieved, 0.52 kg of additional potassium persulfate solution was added. This first stage of the polymerization was carried out during a period of approximately 2 1/2 hours. This first-stage polymerization resulted in the production of a seed polymer latex that was used in the second stage of the polymerization. In the second stage of the polymerization, -1.49 kg of acrylonitrile, 3.47 kg of styrene, 0.050 kg of divinylbenzene, and 9.3 mg of t-dodecyl mercaptan were charged to the reactor containing the seed polymer latex. The temperature of the reactor was then raised to 70 ° C and the polymerization was allowed to continue. After the polymerization was completed, the latex-made coagulated and a dry rubber was recovered.

Example 7 In this experiment, a rubbery polymer was made in a 2 liter glass reactor using the technique of this invention. In the process, 1126 g of water, 5.93 g of a 50% aqueous solution of potassium hydroxide, 14.0 g of hexadecyl monomaleate, 1.0 g were used. of a 30% solution of d deci sodium bicarbensulfonate, 1.0 g of sodium pyrophosphate, 231 g of n-buty lacrylate, 105 g of acrylonitrile, 42 g of 2-ethylhexU acrylate, 42 g of methylacrine, 8.4 g g of 1, 4-butanediol dimethacrylate, 0.48 g of t-dodecylmetacri 1 ato, 8.3 g of a 5% aqueous solution of triethanolamine, and 24.9 g of a 5% aqueous solution of potassium persulfate were initially charged to the reactor. S maintained a temperature of about 35 ° C during the first stage of the polymerization. When a solids content of about 20% was reached, the reaction temperature was increased to about 60 ° C and 24 charged to the reactor with 24 g of additional acrylonitrile, 56 g of styrene, 0.96 g of divinylbenzene, and 0.16 g of t- dodeci lmercaptano. After the reaction was completed, the made latex was coagulated and a rubber was recovered.

EXAMPLE 8 In this experiment, a rubbery polymer was made in a 2 liter glass reactor using the technique of this invention. In the procedure, 1126 g of water, 5.93 g of a 50% aqueous solution of potassium hydroxide, 14.0 g of hexadecyl monomaleate, 1.0 g of a 30% solution of sodium dodecyl sulfonate, 1.0 g of sodium pyrophosphate were used. sodium. 168 g of n-bu-tilacrylate, 105 g of acrylonitrile, 105 g. of 2-ethyl-1-hexy-1-ac-1-a-to, 42-g of methyl lacrylate, 6.3-g of 1,4-butanediol dimethacrylate, 0.44 g of t-dodecylmethacrylate, 8.3 g of an aqueous solution of - 5% triethanola ina, and 24.9 g of a 5% aqueous solution of potassium persulfate were initially charged to the reactor. A temperature of about 35 ° C was maintained during the first stage of the polymerization. When a solids content of about 20% was reached, the reaction temperature was increased to about 60 ° C. and 24 g of additional acrylonitrile, 56 g of styrene, 0.96 g of divinylbenzene and 0.16 g of t-dodecyl mercaptan were charged to the reactor. After the imerization pool was completed, the made latex was coagulated and a rubber was recovered.

Examples 9-12 In this series of experiments, leather-like compositions were made by mixing the rubbery polymers made in Examples 1, 6, 7 and 8 in PVC. The process used 40 parts of the rubbery polymer blended into 100 parts of the PVC. The mixtures made also included 50 parts in DOP and 3 parts of Ba / Zn. The mixtures were made by mixing the components in a -molino at 180 ° C for 6 minutes and then pressing them into samples at 180 ° C. The samples made then were tested to determine their physical properties. The physical properties of the samples made are reported in Table II. The mixture made in Example 9 contained the rubber composition of Example 1, the mixture of Example 10 co had the rubber composition of Example 6, the mixture of Example 11 contained the rubber composition of Example 7, and the mixture of Example 12 contained the rubber composition of Example 8.

Table II Module Hardness Resistance 50% 100% Example Shore to Tension (MPa) (MPa) 9 80 17.0, MPA 275% 6.8 9.0 10 80 16.4 MPA 258% 5.7 8.8 11 80 15.5 MPA 270% 5.2 7.8 12 80 16.3 MPA 260% 6.1 9.4 As can be seen from Table II, all the rubbery pohros made in the Examples 1, 6, 7 and 8 could be made towards leather-like compositions that had good physical properties. In fact, the leather-like compositions made exhibited an excellent combination of properties for use in making skins for use in interior-automobile panels, such as shock pads.

Example 13 In this experiment, the latex made in Example 1 was deodorized before being coagulated. This was achieved by adding 0.5 weight percent (based on total weight of latex) of ethanolamine to the latex at room temperature (approximately 229C). After a day, the residual acrylonitrile level dropped from 1480 ppm to 51 ppm and the low residual n-buty lacrolite level from 325 ppm to -30 ppm. After three days, the level of residual n-buti 1 acrylaterate became undetectable. The deodorized latex was subsequently coagulated and a dry rubber was recovered. The residual levels of acrylonitrile and n-buty lacrylate were too low to be detectable by gas chromatography in the dry rubber. The recovered dry rubber did not have an undesirable odor.

EXAMPLE 14 In this experiment, the procedure described in Example 1 was repeated, except that 0.92 kg of maleate-medium ester soap was replaced with 0.612 kg of an aromatic formaldehyde condensation product soap. The procedure employed in this experiment also differed from the procedure described in Example 1n in that the sodium dodecyl-1-benzenesulfone level was increased to 0.3 kg. The aromatic formaldehyde condensation product soap used in this experiment was the sodium salt of the condensation product of naphthalene sulfonic acid and formaldehyde. It had a molecular weight that was within the range of about 1000 to about 5000 and can be represented by the structural formula: The rubbery polymer then made was tested for haze characteristics. In the procedure used, the condensate of a 10-gram sample held at 100 ° C was captured for 16 hours in a thin sheet of chilled aluminic which was supported on a glass plate. After the 16-hour period, it was determined gravimetrically that 0.3 mg of the condensate had formed. In this way, the cloudiness characteristics of the rubbery polymer made in this experiment were much better than the characteristics of the nebulosity of the rubbery polymer synthesized in Example 1, where 4.0 mg of condemned was recovered in the nebulosity test. In other words, the rubbery polymer made from this experiment generated less than -10% of the amount of mist generated with the rubbery polymer of Example 1.

EXAMPLE 15 In this experiment the procedure described in Example 1 was repeated, except that the 0.92 kg of half-ester maleate soap was replaced with 0.86 kg of a Sokalan polycarboxylate soap. The procedure employed in this experiment was also different from the procedure described in Example 1 in that the sodium dodecyl lbensulfonate level was increased to 0.306 kg. The rubbery polymer then made was tested for haze characteristics. In the procedure used, the condensate of a 10-gram sample held at 100 ° C was captured for 16 hours over a thin sheet of chilled aluminum that was supported on a glass plate. After the 16-hour period, it was determined gravimetrically that 0.4 mg of condensate had been formed. In this way, the haze characteristics of the rubbery polymer made in this experiment were much better than the haze characteristics of the rubbery polymer synthesized in Example 1.

Comparative Example 16 In this experiment the procedure described in Example 1 was repeated, except that the 0.92 kg of medium ester maleate soap was replaced with 0.612 kg of disulfonate soap of didodecyl diphenyloxide Dowfax 2A1. The rubbery polymer made was tested for haze characteristics. In the procedure used, the condensate from a 10-gram sample held at 100 ° C was captured for 16 hours in a thin sheet of chilled water that was supported on a glass plate. After the 16-hour period, it was determined gravimetrically that 1.2 mg to 2.0 mg of condensate had been formed. In this way, the haze characteristics of the rubbery polymer made - in this experiment were somewhat better than the characteristics - of nebulosity of the rubbery polymer synthesized in Example 1, but lower than the results achieved in Examples 14 and 15. Even though have shown certain modalities and representative details for the purpose of illustrating the present invention, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the scope of the present invention.

Claims (22)

CLAIMS:

1. - A process for preparing a low cloudiness rubbery polymer that can be mixed with polyvinyl chloride to make leather-like compositions having good heat resistance and ultraviolet light, the process being characterized in that it comprises the steps of (1) polymerizing (a) buti lacri lato, (b) at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methylacri lato and ethyl lactide, (c) acrylonitrile, (d) a crosslinking agent, and 9e) a surfactant selected from the group consisting of sulfonates and sulfate derivatives; and (f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and p-1-carboxylates, under polymerization conditions. by emulsion - to produce a latex containing seed polymers; (2) add (a) styrene, (b) additional acrylonitrile, and (c) additional binding agent to the latex containing seed polymer under emulsion polymerization conditions resulting in the formation of an emulsion containing the rubbery polymer; (3) add an aminoalcohol to the emulsion containing the rubbery polymer; and (4) recovering the rubbery polymer from the emulsion containing the rubbery polymer. 2.- A low nebulosity rubbery polymer that can be mixed with polyvinyl chloride to make leather-like compositions that have good resistance to heat and light-ultra violet, the rubbery polymer being characterized in that it is comprised of (a) buty lacrylate, (b) at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methacrylate, and ethyl alcohol, (c) acrylonitrile, (d) styrene, (e) a selected surfactant. from the group consisting of sulfonates and sulfate derivatives, (f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylates, and (g) a crosslinking agent. 3. A procedure for preparing a low-cloudiness rubbery polymer that can be mixed with polyvinyl chloride to make leather-like compositions having good resistance to heat and ultraviolet light, the method being characterized in that it comprises the steps of (1) ) polymerizing (a) butyl lactide, (b) at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methyl lactide and ethyl ester, (c) acrylonitrile, (d) an agent of crosslinking, (e) a surfactant agnete selected from the group consisting of sulphonates and sulfate derivatives, and (f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylates, under emulsion polymerization to produce a latex containing seed polymer; 92) add (a) styrene, (b) additional acrylonitrile, and (c) add additional reticulation to latex containing low seed polymer-emulsion polymerization conditions resulting in the formation of an emulsion containing the polymer rubbery and (3) recovering the rubbery polymer from the emulsion containing rubbery polymer. 4. A composition similar to leather that is useful in automotive applications characterized in that it is comprised of (1) polyvinyl chloride, (2) an astifling catalyst, and (3) a rubbery polymer that is comprised of repetitive units that they are comprised of (a) buti lacri 1 ato, (b) at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methylacri 1 ato and et i 1 acr i 1 ato, (c) acrylonitrile, ( d) styrene, (e) a surfactant selected from the group consisting of sulphonates and sulfate derivatives, (f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and p 1 icarboxylates, and (g) a crosslinking agent. 5.- A panel for automotive applications that is of low nebulosity and that is comprised of a semi-rigid urethane foam that is supported by a rigid reinforcement, in which the semi-rigid urethane foam is covered with a skin similar to the leather that characterizes because is comprised of (1) polyvinyl chloride, (2) a plasticizer, and (3) a rubbery polymer that is comprised of repeating units that are comprised of (a) butyl acrylate, (b) at least one member is selected from the group consisting of methyl methacrylate, methyl methacrylate, methyl lactide and ethyl lactide, (c) acrylonitrile, (d) styrene, (e) a surfactant selected from the group consisting of sulfonates and sulfate derivatives, (f) a dispersant selected from the group consisting of condensation products of aromatic formaldehyde and polycarboxylates, and (g) a crosslinking agent. 6. A leather-like composition as set forth in claim 4, characterized in that the composition contains from about 40 to about 160 parts by weight of the rubbery polymer, from about 10 to about 50 parts by weight of the plasticizer. , and from about 0.1 to about 5 parts by weight of antidegradants. 7. A composition similar to leather as specified in claim 6, characterized in that the leather-like composition is also comprised of around 15 to approximately 80 parts weight of acri lonitri lo-buta-diene-styrene resin per 100 parts of polyvinyl chloride. 8. A composition similar to the leather as specified in claim 7, characterized in that the cajecuiced polymer is comprised of repetitive units that are derived from about 40 to about 80 weight percent of bu-tilacrylate, from about from about 5 to about 35 weight percent of a member selected from the group consisting of methyl methacrylate, ethyl methacrylate, methacrylate, and ethylacrylate, from about 4 to about 30 percent. by weight of acrylonitrile, from about 3 to about 25 weight percent of styrene, and from about 0.25 to about 8-weight percent of crosslinking agent. 9. A leather-like composition as specified in claim 8, characterized in that the cross-linking agent is selected from the group consisting of difunctional acrylates, trifunctional acrylates, difunctional methacrylates, trifunctional methacrylates and divinylbenzene. 10. A composition similar to leather as specified in claim 9, characterized in that the leather-like composition contains from about 60 to about 120 parts by weight of the rubbery polymer, from about 15 to about 40 parts. by weight of the plasticizer, and from about 0.5 to 3 parts by weight of antidegradants. 11. A leather-like composition as specified in the filler 10, characterized in that the rubbery composition contains from about 25 to about 55 parts by weight of the acrylonitrile-butadiene-styrene resin per 100 parts by weight. weight of polyvinyl chloride. 1

2. A composition similar to leather as specified in claim 11, characterized in that it is further comprised of an agent that imparts color selected from the group consisting of dyes and pigments. 1

3. A composition similar to leather as specified in claim 12, characterized in that the rubbery polymer contains repeating units derived from about 50 to about 80 weight percent butyl acrylate, or optionally a mixture of buti lacri lato and 2-ethylhexamethia lactal containing up to about 40% of 2-ethylhexyl lacrylate, from about 3 to about 25 weight percent of a member selected from the group consisting of methyl- methacrylate, ethyl methacrylate, methylacrylate and ethyl lactide, from about 6 to about 25 weight percent acrylonitrile, from about 5 to about 18 weight percent styrene, and from about 0.5 to about 4 weight percent. percent by weight of crosslinking agent. 1

4. A composition similar to leather as specified in claim 13, characterized in that the leather-like composition contains from about 70 to about 90 weight percent of the rubbery polymer, from about 20 to about 30 percent by weight. % by weight of plasticizer, air of 1 to 2 weight percent of antidegradant and from about 30 to 40 weight percent of acrylonitrile-lo-bu-tadiene-styrene resin, per 100 parts by weight Weight of polyvinyl chloride. 1

5. A composition similar to leather as specified in claim 14, characterized in that the rubbery polymer is comprised of repeating units that are derived from 55 to about 75 weight percent butyl acrylate, or optionally a mixture of buti lacri lato and 2-eti 1 hexi lacrj_ lato containing up to about 40% 2-ethylhexyl acrylate, from about 5 to about 20 percent by weight methyl methacrylate, from about 10 to about 14 percent. weight percent acrylonitrile, from about 8 to about 14 weight percent styrene, and from about 1 to about 3 weight percent crosslinking agent. 1

6. A composition similar to leather as specified in claim 15, characterized in that the cross-linking agent is one or more members selected from the group consisting of divinylbenzene and 1,4-butanediol dimethacrylate. 1

7. A process as specified in claim 3, further characterized by drying the rubbery polymer recovered from the emulsion and subsequently converting to a powder. 1

8. A procedure as specified in claim 17, characterized in that the rubbery polymer is converted into a powder in the presence of a dividing agent. 1

9. A process as specified in claim 18, characterized in that the dividing agent is selected from the group consisting of calcium carbonate, polyvinyl chloride in emulsion and silica. 20. A procedure as specified in claim 2, characterized in that the 2-ethylhexamethylurea is additionally polymerized in an amount up to 40 weight percent of the total amount of butyl alcohol and 2% by weight. -eti lhexi lacri lato polymerized. 21. A procedure as specified in claim 1, characterized in that the aminoalcohol has the structural formula H0-A-NH2, wherein A represents an alkylene group containing from 2 to about 10 carbon atoms. 22. A procedure as specified in claim 1, characterized in that the aminoalcohol is ethanolamine.