Acrylonitrile polymers with anti-static properties
United States Patent [1 1 Radlmann et al.  
 [451 Apr. 1, 1975 ACRYLONITRILE POLYMERS WITI-I ANTI-STATIC PROPERTIES [75] Inventors: Eduard Radlmann; Gunther Nischk,  
 both of Dormagen, Germany [73] Assignee: Bayer Aktiengesellschat&#39;t,  
 Leverkusen, Germany 22 Filed: Apr. 13, 1973 21 Appl. No.: 350,959  
 [30] Foreign Application Priority Data Apr. 14, 1972 Germany 22l7974 [58] Field of Search.,... 260/85.5 R, 85.5 D, 88.7 R, 260/88.7 D, DIG. l5, DIG. l6, DIG. 19, 45.85 N, 45.85 P, 45.9 P, 45.95 R, 45.95 C,  
 [56] References Cited UNITED STATES PATENTS 3,737,420 6/1973 Brokmeier et al...... 260/85.5 R V 3,743,685 7/1973 Grosjean et al 260/DIG. 15  
 Primary Examiner,-I larry Wong, Jr. Attorney, Agent, or FirmPlumley &amp; Tyner [5 7] ABSTRACT I The invention relates to acrylonitrile polymers or copolymers containing as an anti-static agent from 1 to 20 percent by weight based on the mixture as a whole of polyalkylene oxide derivatives with terminal sulphonate groups attached through alkylphenyl ether groups.  
 6 Claims, No Drawings ACRYLONITRILE POLYMERS WITH ANTI-STATIC PROPERTIES This invention relates to acrylonitrile polymers with reduced surface resistance.  
  Since the surface resistance of shaped articles, especially fibres, of polyacrylonitrile or acrylonitrile copolymers is greater than 10 Ohms, the potential commercial applications of materials of this kind are limited on account of the extremely troublesome electrical charge.  
  There is an extensive literature on tests to provide acrylonitrile-based polymers with an anti-static finish, such as applying anti-statically active substances to the surface of the shaped articles, introducing suitable substrates into the melt or solution of the polymers, followed by forrning, or copolymerising the acrylonitrile with anti-statically active comonomers, in such a way that their surface resistance falls to values below 10 Ohms.  
  A permanent anti-static effect can seldom be obtained by applying suitable compounds because shaped articles are generally exposed to mechanical or solvolytic influences which remove the surface coating. Acrylonitrile copolymers with comonomers which&#39;reduce surface resistance should have the most favourable antistatic effect because the active constituents are firmly anchored in the polymer chain. In this case, however, considerable difficulties are encountered during polymerisation in the case of conventional systems.  
 No problems are involved in adding anti-statically active substrates before the forming stage. The requirements which substances of this kind have to satisfy include high compatibility with the polymer, resistance to temperature stressing, resistance to evaporation, hydrolytic influences or washing out with water or organic solvents.  
 &#39; Conventional anit-static additives are based on compounds from such classes as ureas, dithiocarbonates, phosphoric acid amides, aminocarboxylic acid amides, polyethylene oxides, and oxalkylated aliphatic or aromatic alcohols with terminal sulphonate groups which are introduced through aliphatic ether groups with sultones or w-halogen alkane sulphonates.  
  It has now been found that polyalkylene oxide derivatives with terminal sulphonate groups attached through alkylphenyl ether groups show outstanding anti-static activity as additives to acrylonitrile polymers. The reduction which these additives produce in electrical surface resistance is also obtained in some other synthetic polymers.  
  According to the invention there is provided a compound corresponding to the general formula (I) m is an integer of from 1 to 150;  
 M represents a member selected from the group consisting of an alkali metal, alkaline earth metal, an ammonium radical and an alkylammonium radical;  
 R represents hydrogen or a methyl radical;  
 5 R represents a member selected from the group consisting of, hydrogen, a lower alkyl radical with from 1 to 6 carbon atoms, fluorine, chlorine, bromine and iodine;  
 R represents a member selected from the group con- 10 sisting of hydrogen, Nl-l NO CN, CF  
 Cl and R R I l SO O-CH-CH A in which R, M and m are defined above; and A represents a radical selected from the group consisting of O $3 R 0-, R -N, R -N B -c-0-, (111) (IV). (v) -(v1) 1 2 (VII M0 R&#39; R 40 l l R 0-CH-CH 0-R ,-O  
  R M0 5 n 0 o l H ll R CH-CH U-C-R -CO 2 1 I R in which R, R R M and m are as defined above, R represents a radical selected from the group consisting of an alkyl radical with from 1 to 30 carbon atoms, an aryl, alkylaryl and arylalkyl radical, and R represents a number selected from an alkylene radical with from 1 to 30 carbon atoms and an arylene radical; and n represents the number 1 or 2.  
  so 14 1} 3 e A H-GH- 2 (I) in which A, R, R R M, m and n are as defined above, and spinning the solution or melt.  
  The novel anti-static agents added in accordance with the invention are prepared by converting polyether diols of ethylene oxide or propylene oxide or oxalkylation products, preferably with ethylene oxide, propylene oxide or mixtures of the two reacted aliphatic or aromatic alcohols and diols, primary or secondary aliphatic or aromatic amines, monoor dicarboxylic acids corresponding to the general formula in which B represents the radicals HO, R -,-O-,  
 R R R o I 03 Gil-0%!!- ig 1 o&#34; v 9 u Q or H O-CH-CH O-O-R -O-O- and R, R R 3: and m are as defined above, into the corresponding alcoholates in the presence of an inert gas and in the absence of moisture, and reacting the resulting alcoholates at temperatures of from 20to 150C, either in the melt or in an inert solvent, with a compound corresponding to the general formula (XI):  
 08 a a-B Ha]. R XI) in which R,, R and M are as defined above, and Hal represents fluorine, chlorine or bromine, accompanied by the elimination of M-Hal.  
  The types in which R represents NH are obtained from the corresponding nitro compounds by catalytic hydrogenation with Raney nickel.  
 The following are mentioned as examples of oxalkylation products for the production of the new anti-static agents added in accordance with the invention:  
 . co ea k 9 I 1 O The following are examples of activated halogen shows a neutral reaction. The alkali metal halide compounds for the nucleophilic substitution reaction formed during the reaction is then isolated by filtration. according to the invention: Examples of suitable inert solvents include benzene,  
  dioxan, dimethyl formamide, dimethyl acetamide or 5 N-methyl pyrrolidone. Nitrogen, hydrogen or helium 3 F 2 can be used as the inert gas.  
 . The following are mentioned as examples of the antistatic additives according to the invention: R0 3 3 c1 0 cn -(cri )o{m -cn so m Q M.- 1 80 8a. p  
 $0 1k 80 Na 0 89. C1 80 C1 Q ll cB H -O 0H -0H N0 1e 35 The anti-static agents can be prepared for example as 01 c1 follows:  
  For conversion into the alcoholate, the corresponding oxalkylation product is either reacted in the melt CHZ-CHQ- with an equimolecular quantity of an alkali metal or has H c 2 a calculated quantity of the alcoholate of a low-boiling 1&#39;9 9 c1 c1 alcohol, for example methanol or ethanol, added to it M Na 5 3N8.  
  3 o n-(o-cn -cngoen on -cn n0 in the absence of moisture and in an inert gas atmosphere, followed by removal of the methanol or ethanol by distillation under reduced pressure. The alcoholate 2 N0 is then reacted either in the melt or in an inert solvent 65 with the activated aromatic halogen compoundat tem- L10 8 o-cfl -cflgq) 30 Li peratures of from 20 to C. In most cases, the reac- 3 no 3 tion is exothermic so that it is advisible to cool the reaction mixture. The reaction is over when the mixture so Na The anti-static compounds according to the invention are compatible with solutions of acrylonitrile polymers, i.e. do not show any disintegration phenomena. Stabilisers, fillers, dyes, pigments, anti-oxidants or the like can also be added without causing disintegration or reduction of the anti-electrostatic effect. The mixtures can readily be processed into filaments or films.  
  In addition to pure polyacrylonitrile, acrylonitrile polymers suitable for the purposes of the invention include those which contain at least 60 percent by weight of polymerised acrylonitrile and less than 40 percent by weight of other copolymerisable compounds from the group of vinyl and (meth) acryl compounds in copolymerised form. The following are mentioned as examples of copolymerisable compounds: (meth) acrylic acid esters, (meth) acrylic acid amides, vinyl chloride, vinylidene chloride, and also copolymerisable compounds of the kind which bring about an improvement in affinity for acid or basic dyes as described in US.  
 .Pat. Nos. 2,649,438; 2,837,500; 2,837,501; 2,895,949  
 and 2,687,938.  
  Suitable solvents for the polymers include any of the solvents which can be used for polyacrylonitrile, especially dimethyl formamide.  
  It is considerably advantageous that fibres containing the anti-static agents according to the invention do not undergo any appreciable changes in their surface resistance, even after repeated washing with alkaline washing agents.  
  In addition to their outstanding anti-static effect, the acrylonitrile polymers according to the invention are distinguished by their high affinity for basic dyes and by their considerably improved water absorption.  
 - In the following production specifications and Examples, parts by weight are to parts by volume as kilograms to litres.  
 Production of the anti-static additives A. 5.4 parts by weight of sodium methylate are added to 121.4 parts by weight of an anhydrous e thoxylated stearyl alcohol (average molecular weight Mn 1214, determined from the OH-number) in 150 parts by volume of absolute methanol. Following removal of the methanol in a water jet pump vacuum at 70C, the mixture is cooled to room temperature. 26.0 parts by weight of sodium 3-nitro-4-chloro-(1 )-benzene sulphonate are then introduced in portions into the melt while dry nitrogen is passed over. The temperature is kept at 65C by cooling. On completion of the reaction (a sample of the reaction mixture diluted with water gives a pH value of 7) the reaction mixture is dissolved in 144 parts by weight of anhydrous &#39;dimethyl formamide containing some active carbon and separated from the sodium chloride by filtration. Following removal of the solvent, a yellow coloured product, wax-like at room temperature, is obtained in a quantitative yield. It has the following constitution:  
  ca maw-m cn 1 1 7 B. 4.6 parts by weight of metallic sodium are dissolved in 208 parts by weight of an oxethylated isononylphenol (average molecular weight IVIn 1040, determined from the OI-I-number) at 120C while dry nitrogen is passed over. The alcoholate is then dissolved. in 253 parts by weight of anhydrous dimethyl formamide, followed by the addition in portions at room temperature of 51.9 parts by weight of sodium 3-nitro-4-chloro-(l)-benzene sulphonate while dry nitrogen is passed over. The temperature is kept at C by cooling. On completion of the reaction (neutral reaction of the reaction mixture), the mixture is isolated from the sodium chloride by filtration and the solution hydrogenated in an autoclave with 40 parts by weight of Raney nickel at a temperature of C and under a hydrogen pressure of 63 atms. Removal of the Raney nickel and the solvent leaves 245 parts by weight of a substantially colourless product, liquid at room temperature, with the following constitution:  
 i C. 4.6 parts by weight of sodium are added to 206 parts by weight of anhydrous ethoxylated N- methylstearylamine (average molecular weight Mn SO Na 1030, determined from the OH-number) while dry nitrogen is passed over, followed by stirring at l 10C until a solution is obtained. Following dissolution of the alcoholate in 300 parts by weight of dry dimethyl formamide, 51.9 parts by weight of sodium 3-nitro-6-chloro- (l)-benzene sulphonate are added in portions in such a way that the temperature does not exceed 65C. When the reaction mixture shows a neutral reaction, the mixture is filtered off from the sodium chloride precipitated and the solvent removed in vacuo, leaving behind, in a quantitative yield, a yellow coloured product, liquid at room temperature, with the following compos1tion:  
  D. 212 parts by weight of a segment polyaddition product with an average molecular weight of Mn 1060, obtained by reacting propylene oxide with a polyethylene glycol (17in 480), are reacted with 9.2 parts by weight of sodium in 500 parts by volume of absolute dioxan at reflux temperature while nitrogen is passed over. After the evolution of hydrogen has stopped, 103.8 parts by weight of sodium 3-nitro-6- chloro-( l )-benzene sulphonate are added in portions at 70C. After 5 hours, the reaction mixture shows a neutral reaction. The reaction mixture is then filtered off from the sodium chloride formed and the dioxan distilled off in vacuo, leaving behind in a quantitative yield a pale brown coloured wax-like substance of the following composition.  
 SO Na E. 10.8 parts by weight of sodium methylate are added to 150 parts by weight of anhydrous ethoxylatecl isononylphenol (average molecular weight Mn 750, determined from the Ol-l-number) in 50 parts by volume of methanol. Following removal of the methanol in vacuo, 98.2 parts by weight of disodium 4,4- dichlorodiphenyl sulphone-( 3,3 )-sulphonate are introduced in portions into the melt with cooling at 65 to 70C while nitrogen is passed over. On completion of the reaction, the reaction mixture is dissolved in 400 parts by volume of dimethyl formamide, filtered off from the sodium chloride and the solvent removed by vacuum distillation, leaving behind in a quantitative yield a pale yellow coloured product, liquid at room temperature, with the following composition:  
  The following Examples are to further illustrate the invention without limiting it.  
 EXAMPLE 1 The anti-static agents described in A-E are added in different quantities to a 27 percent dimethyl formamide solution of a polyacrylonitrile polymer (K-value according to Fikentscher of 94 parts by weight of acrylonitrile, 5 parts by weight of acrylic acid methyl ester and 1 part by weight of the sodium salt of methallyl sulphonic acid. The solutions are spun in a known manner by the dry-spinning process. After conditioning at 23C/50 percent relative humidity, the surface resistance of the stretched filaments is measured. After the initial surface resistance has been determined, the filaments are washed at 40C with a 0.5 percent solution of a standard detergent. The filaments are dried and reconditioned before the subsequent measurement.  
  The results are set out in Table l below and compared with those of filaments of the aforementioned copolymer without any anti-static additions.  
  ln-the same way as described in Example 1, the antistatic agents described in A-E are added in different quantities to a 27 percent dimethyl formamide solution of a polyacrylonitrile copolymer (K-value 80) of 61.3 parts by weight of acrylonitrile, 37 parts by weight of vinylidene chloride and 1.7 parts by weight of the sodium salt of methallyl sulphonic acid. As in Example 1, the solutions are spun into filaments, the surface resistance of the filaments determined and the filaments washed. The results obtained are set out in Table 2:  
 Table 2 R R l l (11) Anti-static Surface resistance at 23&#34;( 50% -S02 O-CH-CH A 7 addition relative humidity [(2] after after after 5 E slrctchwashes washes ing S0 M 1 I I III III 2; y weight 10 in which R, M and m are defined as above; and  
  of A 7-10 940&#39;&#34; no&#34; A is 8 71 by weight IO 01&#39; a 910&#39;&#34; a-m&#39;&#34; 9-10 10 n h ll nip 2 10&#39;&#34; 410&#39;&#34; (no O X &#39;71 by weight m D 910&#39;&#34; H0&#34; H0&#34; R O -N- I R3-c.-O.. ll) by weight H m m oih 2-10 4-10 510 (III) (IV) (v) (VI) R M0 s f R 7 I1 O-CH-CH 0R -0-,  
 in 1 2 n MO s R1 M0 5 R1 3 R n a n R 0 o I I l I II II R -CH-CH N- or R O-CH-CH U-C-R -C-O- a a 1 2 1 R We claim: in which R, R R M and m are defined as above; 1. A polymer composition comprising an acryloniand trile polymer and as an antistatic agent therefor for 1 R is an alkyl radical with 1 to carbon atoms, an  
 solids Content 0f at 40 aryl, alkylaryl or arylalkyl radical;  
 R is an alkylene radical with 1 to 30 carbon atoms or an arylene radical; and  
 n is the number I or 2.  
 2. The composition of claim 1 in which said acryloni- S0 M R n 3 l5 trile polymer comprises at least percent by weight I l of acrylonitrile and up to 40 percent by weight of at A 2 least one vinyl compound which is copolymerizable E with acrylonitrile.  
  1 3. The composition of claim 2 in which said vinyl 2 so compound copolymerizable with acrylonitrile is an acrylic acid ester, an acrylic acid amide, a methacrylic in which acid ester, a methacrylic acid amide, vinyl chloride, vim is an integer f f om 1 m nyhdene Chl0l&#39;ld 0&#39;l a mixture thereof. M is an alkali metal, an ammonium radical, or an al- 55 4. The composition of claim 1 in which said antikylammonium di l; static agent has the formula to 20 percent by weight of the total least one compound having the formula 5. The composition of claim 1 in the form of a film.  
 R is a h dro en or methyl; I I R, is hyd roge n, lower alkyl radical with l to 6 carbon 6; 6. The composition of claim 1 in the form of a filaatoms, fluorine, chlorine. bromine or iodine; ment. R is hydrogen. z 2 C1 or