[1]Uni'ted -States Patetit Office 3y7O,l@765 3,701,765 ANIISTATIC MOLDING COMPOSMONS and KarI-Heinz Magosch and Konrad Rombusch, Marl5 Ursula Eichers, ReckHnghausen, Germany, ass'gnors 5 to Chemische Werke Huls A.G., Marl, German) No Drawing. F.Hed Oct. 28, 1970, Ser. No. 84,886 Clainis priority, application Germany, Oct. 29, 1969, P 19 54 291.7; Jan. 19, 1970, P 20 02 095.5 int. Cl. C08f 29102, 29104 U.S. Cl. 260-93.7 23 Claims 10 ABSTRACT OF THE DISCLOSURE Antistatic pdlyolefin molding compositions and articlescontaining 0.01-5.0% by weight of an antistat of the for- 15 mula: N-CH2 R2--c CH2 N-CH2 20 I .Kl (I) wherein RI is hydrogen, alkyl or alkenyl of 1-5 carbon atoms, or a group of the formula (C.H2,0),,H in which x is 2 or 3 and n is 1-10, and wherein R2 iS straight chain 25 or branched alkyl or alkenyl of 5-25 carbon atoms, inclusive. BACKGROUND@ OF THE INVENTION 30 This invention relates to antistatic polyolefin molding compositions and shaped articles thereof. Polyolefin products tend to attract dust to a large degree during storage and use as a result of electrostatic charging, which considerably diminishes their utility value. 35 Various means have been suggested to avoid these difficulties. Thus, it is possible to coat the surfaces of shaped polyethylene articles with a material which thus reduces electrostatic charging. However, such processes usually have the disadvantage that the effectiveness is lost as soon 40 as the antistatic coating is worn off by use or cleaning. A more lasting effect is attained by incorporating the antistatic additive into the polymeric substance, and producing shaped articles from these mixtures. Among this group of additives belong, for example, quaternary am- 45 monium salts, polyalkylene glycols, and polyalkylene glycol esters. Better results are achieved with oxyethylates of - alkanols and alkylaryl phenols. (See Belgian Pat. 536,623 and British Pat. 731,728). However, these compounds tend to 50 bleed out when incorporated into the plastic article in an amotint sufficient to achieve a satisfactory effect. A further increase in antistatic effectiveness can be obtained employing nitrogen-containing compounds, such as, for example, amides and aminocarboxylic acid derivatives 55 (French Pats. 1,377,803-808), oxazolines, and imidazolines, and, to a still grcater extent, with alkylamines (Belgian Pats. 655,182 and 655,183), especially oxyethylates of alkylamines (Belgian Pat. 645,80D; French Pats. 1,345,- 827 and 1,322,626; German published application DAS (io 1,228,056), the bishydroxyethyl derivatives being the most effective antistatics of all those described heretofore. However, these compounds often have the disadvantage that, in the first few days after the manufacture of the molded polyolefin article, film, filament or fiber, the additive 65 does not immediately achieve its full antistatic - effectiveness. The term "molded articles" as used herein means the shaped, compact products of injection-molding, - extrusion, and deep-drawing processes, as distinguished from films, filaments and fibers. The result is that the electrostatic 70 charge which develops during processing and which generally is very high, for example during separation from the Patented Oct. 31, 1972 2 mold in injection molding processes, cannot dissipate immediately, so that, within a few days, the molded articles become unattractive due to dust attraction. The situation is aggravated by the large amount of dust usually present in factory workshops. A special problem is presented in the antistatic treatment of films, threads and fibers of polyolefins. It is known to those skilled in the art that, in order to obtain an antistatic effectiveness, it is important that the surface of the molded aricles be coated with the antistat compound. This surface coating is considerably smaller in case of threads and fibers than in case of injection-molded, extruded, and deep-drawn atticles, after admixing the same amount by weight of antistat, due to the fact that the surface area of threads and fibers is very large as related to the weight thereof. Accordingly, it is to be expected that the effectiveness of an antistatic agent in threads and fibers commences only after uneconomically large amounts have been added thereto. Such a behavior is also usually observed. Consequently, there is a special need for antistatic agents which become effective in fibers already at low amounts of addition. Especially valuable would be an agent of this type which protects, in the same range of concentration, compact molded articles as well as fibers, so that it is possible to utilize the same molding composition for a great variety of manufacturing fields. A large number of 2-fatty alkyl oxazolines and imidazolines, as well as the Nderivatives thereof, are described in the patent literature. In contrast thereto, of the tetrahydropyrimidines, there are disclosed only specific esters with other heterocyclic compounds, for example (U.S. 3,020,276): CH2-N c@, C-(CH2)@COOR" CH2-N CH2-N CH2 C-R, CH2-N @H2CH2--OCOR" wherein R' is alkyl as C12H25 and R" is CH2---CH2 -CH2-CH2-N \ c R with R7--alkyl as C5H,l or C17H33- Copolymers of acrylic or vinyl compounds and N-vinyl tetrahydropyrimidines are also known (Belgian Pat. 625,362). From this state of the art, one skilled in the art would conclude that only complicated tetrahydropyrimidines are effective as antistatic compounds whereas the simple tetrahydropyrimidines, e.g., 2-fatty-alkyl derivatives would be ineffective. Thus, the problem existed of rendering polyolefins antistatic which had the advantages provided by the amine antistatic agents, without the above-mentioned disadvantages of delayed effectiveness and the use of structurally complicated compounds which are not readily accessible. SUMMARY OF THE INVENTION According to this invention, polyolefins are rendered antistatic without the abovedescribed disadvantages associated with the prior art methods, by incorporating there-
[2]3;701)765 3 in from 0.01-5.0% by weight, based on the polyolefin, of a coinpound of the formula: N-CH2 Rr-C \CI12 N-CH2 I wherein RI is hydrogen, alkyl or alkenyl of 1-5 carbon atoms, or a group of the formula (C.H2,O),,H in which x is 2 or 3 and n is 1-10, and wherein R2 iS straight chain or branched alkyl or alkenyl of 5-25 carbon atoms, inclusive. Optionally, an equivalent amount of an organic or inorganic acid can also be incorporated therein. DETAILED, DISCUSSION Polyolefins which can be rendered antistatic according to this invention include high- and low-pressure polymers of ethylene, propylene, butene-1,- pentene-1, etc., especially polyethylenes of a molecular weight from 20,000 tO 150,000, polypropylenes of molecular weights from 100,000 to 800,000, polybutenes-I of molecular weights from 300,000 to 3,000,000, polypentenes-1, and copolymers and mixtures thereof. . Tetrahydropyrimidines of Formula I which can be employed in accordance with this invention are those wherein RI is hydrogen, alkyl or alkenyl, preferably alkyl of 1-5, preferably 1-2, carbon atoms, inclusive, or a group of the formula (C,,H2.0).,,H in which x is the integer 2 or 31 preferably 2, and n is an integer from 1-10, preferably 1-3, inclusive, especially 1; and R2 is strai@ght-chain or branched alkyl or alkenyl, for example of 5-25, preferably 7-17, especially 9-13, carbon atoms, inclusive. Specific examples of groups wherein R, is alkyl or adkenyl are propyl, n-butyl, isobutyl, and butenyl. Preferred are the methyl and ethyl. Specific examples of groups wherein R, is (C.H2,O)nH, are -CH2CH20H, -CH,CH,CH,OH, -CH,CH(CH,).OH -(CH2CH20)2H, -(CH2CH20)3H, -(CH2CH20)5H, etc. Examples of R2 are n-heptyl, n-octyl, trimethylpentyl, n-nonyl, n-undecyll n-undecenyl, isotridecyl, n-tetradecyl, n-pentadecyl, n-heptadecenyl, -and n-heptadecyl. Preferred are n-nonyl, n-decyl, n-undecenyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl and mixtures thereof, such as, for example, a mixture of compounds in which R2 iS Cg- tO Ci3-alkyl. Examples of specific compounds are 1-methyl-2-hepta decyltetrahydropyrimidine, 2 - pentacosyl - tetrahydropyrimidine, I - n -,butyl - 2 - n - hexyl - tetrahydropyrimidine, Iethyl-2-heptadecenyltetrahydropyTimidine, - 1-9hydroxypropyl - 2 - (c& - ethyl) - pentyltetrahydropyrimidine; the condensation product of palmitic acid and H2N(CH2)1- NH-(CH2CH20)loH; the condensation product of caproic acid and H2N(CIE[i)B=Nll- CH-CH20)aH; I (CH3 and I - propenyl @ 2 - heptadecenyltetrahy&opyrimidine,- Especially suitable are 1 - ethyl - 2 - undecyl - tetrahydropyrimidine, I - hydroxyethyl - 2 - undecyl - tetrahydropyrimidine, and mixtures, of 1 - methyl - 2 - alkyl - tetrahydropyrimidines in which the 2-alkyl group is a fatty alkyl group varying from 9 to 13 carbon atoms, inclusive. The compounds of Formula I are conventionally obtained by reacting correspondingly substituted 1,3-propanediamines with carboxylic acids or the derivatives thereof, such as, for example, esters or nitriles. Advantageously, the starting materials are carboxylic acids and 1,3-propanediamines, and the thus-produced water (2 mols per mole of tetrahydropyrimidine) is azeotropically removed from the reaction mixture, the entraining agent preferablv being xylene. 4 In addition to the above method, other methods are known which, however, are not of any practical importance. The tetrahydropyrimidines can be employed in free base form or in the form of acid addition salts, e.g., of monoand dicarboxylic acids, such as, for example, acetic acid, lauric acid, oleic acid, oxalic acid, tartaric acid, succinic acid and 1,12-dodecanedioic acid; hydroxycarboxylic acids, such as, for example, lactic acid, glycolic acid, io and ricinoleic acid; inorganic acids, e.g., sulfuric acid, and partial alkyl esters thereof; sulfonic acids, such as, for example, Ci5-alkane- and C12- alkylbenzenesulfonic acids, whereby the basic character of the compounds is lowered or eliminated. 15 Examples. of such salts are I - ethyl - 2 - undecyl - tetrahydropyrimidine and lactic acid; the salt of 1-hydroxyethyl - 2 - tetradecyl - tetrahydropyrimidine and lauric acid; and the salt of 1-butyl-2-nonyl-tetrahydropyrin-lidine and phosphoric acid. 20 T@-e safts can be prepared by converting the mixture of equimolar amounts of one or more tetrahydropyrimidines and one or more carboxylic acids, optionally with heating, @ into a homogeneous melt by vigorous stirring. The nlixture, if hot, is allowed to cool. Altematively, both 25 components in suitable solvents can be mixed and the conibined solutions evaporated to dryness, which procedure avoids the danger of discoloration of the thus produced salt. The amounts of the above-disclosed antistatics incorpo30 rated into the polyolefins range is usually from 0.01 to 5.0% by weight, based on the polyolefin. Preferred are amounts of from 0.1 to 1.0% by weight, since these amounts provide complete protection against dust accumulation by electrostatic attraction even in case of very 35 dry and warm air, without appreciably impairing the crack resistance of the highly crystalline types of polyolefins. If lower concentrations are employed, for example, 0.005 to 0.009%, based on the polyolefin, the protection against electrostatic charging is substantially 40 lower. Such protection, although insufficient for dry air, may stih be sufficient when the polyolefin is stored in moist air. Higher concentrations than 5.0% are normoy unnecessary since they do not result in any further improvement in antistatic properties. 45 The novel additives can be introduced into the polyolefin in various ways. For example, the polyolefin and the antistatic agent can be directly converted into a homogeneous mass in a mixer. For this purpose, generally any commerciaffy availa-ble high-speed mixer is suitable. It is 50 also possible first to admix in the polyolefin a percentage of the antistatic which is higher than desired, and then provide the desired content of antistatic in this niixture by admixing additional polyolefin lacking the antistatic agent. It is also possible to dissolve, disperse, suspend, 55 or emulsify the antistatic agent in a suitable organic solvent, add the solution, dispersion, suspension, or emulsion to the powdered polyolefin, and vigorously stir the resulting niixture. The solvent can then be removed, for examp le, by distillation. A solvent well suited for these 60 purposes is methanol. However, all other readily distillable solvents for the antistatic agent are suitable for this purpose as well. It is also possible to incorporate the antistatic agent into the polyolefin directly on the rolling mill or , for example, during injection molding in an ex65 truder, e.g., a screw injection molding machine, or in a spinning extruder. It is particularly advantageous to produce a granulatedpolyolefin having a higher than desired concentration of antistat agent, and then reducing to the desired level the 70 antistat content during processing, e.g., by admixing thereto granulated polyolefin which is free of additive. Other additives can be added which are customarily employed in plastics processing, for example, pigments, stabilizers, plasticizers, extenders, and fillers, as well as 75 slip agents.
[3]3,701,765 5 In the case of fibers and filaments, incorporation and homogenization can also be conducted advantageously with the simultaneous addition of 0.01-3.0% by weight, based on the polyolefin, of other conventional antistats, for example, polyethylene and polypropylene glycols, 5 polyols, such as glycerin, as well as the monoethers and monoesters, diethers and diesters, and ether esters thereof, and likewise alkylamines and fatty acid amides. Thus, there can be incorporated into the polyolefin an additional substance which prevents the slight yellowing 10 of the antistats which can occur during prolonged processing at high temperatures. Suitable such stabilizers are, for example, phosphites, especially didecylphenyl phosphite, decyldiphenyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris(nonylphenol+9 mols ethyl15 ene oxide) phosphite. These compounds are usually added in amounts of from 0.01 to 1.0% by weight, based on the polyolefin. Also, the addition of an alkanesulfonate, e.g., sodium pentadecanesulfonate, is of - advantage. For this purpose, approximately 0.05 to 2.0% by weight is re20 quired, based on the polyolefin. The claimed additives are highly effective immediately after the manufacture of the molded article, without forming a troublesome film on the surface of the molded article. This is surprising especially since all analogous 25 compounds previously disclosed as being highly effective antistats for this application, whether open-chain or cyclic, i.e., carboxylic acid amides, imides, and amidines; oxazolines; and imidazolines are substantially inferior with respect to antistatic effectiveness and diffusion rate, com30 pared to the compounds of this invention, so much so they seldom have been employed in commercial applications. Without further elaboration, it is believed that one skilled in the art can, using the preceding description, . . 3autilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. 40 6 EXAMPLES The antistatic behavior of the molded articles was determined by the ash dust testing method in which data as to the dust accumulation to which the test bodies are exposed (a) in a normal atmosphere (normal dust accumulation) and (b) when being sprinkled with a special powder (color powder test); and by measuring the surface resistance according to German Industrial Standard DIN 53,482 VDE 0303, Part 3. These tests were conducted on test dishe@s having an edge length of 42 x 250 x 320 mm. The ash dust test was conducted in the following manner: One hour after producing the test body, it was rubbed ten times vigorously with, in each case, fresh cellulose and then fresh, crushed cigarette ash held 0.5 cm. above the surface. The results of the test are designated as follows: Test body does not attract any ash particles + Minor ash attraction ----------------------- (+) Medium ash attraction --------------------- (+ Moderately strong ash attraction ------------- Strong ash attraction ----------------------- The test is repeated 24 hours and 8 days -after manufacture. In the normal dust accumulation test, the test results are classified semiquantitatively as none, very light, light, mediurn, strong, and very strong dust accumulation, observed 8 days after manufacture. The color powder test, which is conducted one hour, 24 hours, and 8 days after the manufacture of the molded articles, determines how strongly, as determined by the degree of color separation, of the two'components of a mixture of red-dyed sublimed sulfur and blue-dyed lycopodium spores are attracted by different areas of the surface of the plastic, the red areas identifying zones of positive charging and the blue areas identifying zones of negative charging on the surface of the plastic. The asterisk in parentheses ((*)) means Lichtenberg figures were observed. TA13LE I Perce nt Example No.' Polyolefin by weight Antistat 1 -------------- Polyethylene 0.3 1- mothyl-2-heptadecyl-tetrahydropyrimidine. 2 ------------------- do ------------ 0.3 Iethyl-2-heptadecyl-tetrahydropyrirnidine. 3 ------------------- do ------------ 0.3 Conde nsation product of pahnitic acid and H2N-(CH2)3--NH(CH2CH20) IOII4 ------------------- do ------------ 0.3 1- pentyl-2-tridecyl-tetrahydropyrimidine. 5 ------------------- do ------------ 0.3 1- ethyl-2-hexyl-tetrahydropyrimidine. 6 ------------------- do ------------ 0.3 Conde nsation product of olele acid and 112N-(CH2)3-NH-(CH-CH20)OH@H3 7 ------------------- do ----------- 0.3 1- methyl-2-pentacosyl-tetrahydropyrimidine. 8 ------------------- do ------------ 0.3 1- ethyl-2-undecyl-tetrahydropyrimidine. 9 ------------------- do ------------ 0.3 1- butyl-2-Cg-to ci3-fatty alkyl-tetrahydropyrimidine. 10 ------------------ do ------------ 0.3 1- hy&oxyethyl-2-undecyl-tetrahydropyrimidine. 11 ------------------ do ------------ 0.3 1- methyl-2-tridecyl-tetrahy&opyrimidine. 12 ----------------- d ------------ 0.3 Salt of I-ethyl-2-undecyl-tetrahydropyriinidine and lactic acid. 13ii ---------------- do ------------ 0.3 Dode cyl-N, N-dihydroxyethylainine. 14C ---------------- doL ----------- 0.3 Hexyl -N, N-dihydroxyethylamine. 15C ---------------- do ------------ 0.3 Tetra cosyl-N,N-dihy&oxyethylamine. 160 ---------------- do ------------ 0.3 2- undecyl-oxazoline. 17C ---------------- do ------------ 0.3 1- othyl-2-tetracosyl-iiffldazoline. 180 ---------------- do ------------ 0.3 Dode cyloxypropyl-N,N-dihydroxyethylamine. 19C ---------------- do ------------ 0.3 Witho ut additive. 20 ------------- Polypropylene ---- 0.5 1- butyl-2-undecyl-tetrahydropyrinildine. 21 ------------------ do ------------ 0.5 1 ethyl-2-undecyl-tetrahydropyriniidine. 22 ------------------ do ------------ 0.5 ialt of 1-hydroxyethyl-2-tridecyl-tetrahydropyrimidine and lauric acid. 23 ------------------ do ------------ 0.5 Iethyl-2-heptadecyl-tetrahydropyriinidine. 24C ---------------- do ------------ 0.5 Dode cyloxypropyl-N,N-dihydroxyethylaimine. 250 ---------------- do ------------ 0.5 Witho ut additive. 26 ------------- Polybutene-1 ------ 0.5 dine. 27 ------------------ do ------------ 0.5 28 ------------------ do ------------ 0.5 dine. 29 ------------------ do ------------ 0.6 dine. 30C ---------------- do ------------ 0.5 ne. 31C ---------------- do ------------ 0.5 I C = Comparison exainple.
[4]3,701,765 7 TABLEII Ash test after- Normal dust Color powder test-Measure: "color separation" after1 24 8 accumulation No.' hour hours days after 8 days I hour 24 hours 8 days 1 -------- + + Very light --------- Ligbt ------------- Very light --------- None. 2--------- + + ----- do ------------------ do ------------------ do ------------- Do. 3-------- (+) + Light ------------- Medium ----------- Light ------------- Very light. 4-------- + + None -------------- Very light --------- None -------------- None. 5-------- + Light ------------- Medium ----------- Light ------------- Very light. 6 -------- + ----- do - ----------------- do ------------------ do ------------- L)O. 7 -------- + ----- do - ----------------- do ------------------ do ------------- Do. 8 -------- + + + None -------------- None -------------- None -------------- None. -------- (+) + + ----- do ------------- Very light -------------- do ------------- Do. 10 -------+ + + ----- do ------------- None --------- --------- do ------------- Do. 11 -------+ + + ----- do ------------------ do ------------------ do ------------- Do@ 12 ------- + + ----- do ------------- Very light -------------- do ------------- Do@ 13C ----- + + Very light --------- Medium ----------- Light------------- Do. 14C ----- Strong ------------ Strong --------- Strong ------------ Medium. 16C ----- Strong (1) --- ------ Strong -------------- do ------------- Do. 16C ----- Light ------------------ do ------------- Medium ----------- Light. 17C- + + Very light ---- ----- Medium ----------- Light ------------- None. 18c-:----- + + None ------------------- do ------------- Very light --------- Do. 19C ----- Very strong (1) ---- Very strong (*) ---- Very strong (*) ---- Very strong (1). 20--- + + None -------------- Very light --------- None -------------- None. 21 ------ :+ + + ----- do ------------- Noiie ------------------- do ------------- Do. 22 ------- + + ----- do ------------- Very light -------------- do ------------- Do. 23 ------- + + ----- do ------------- Light ------------- Very light --------- Do. 24C ----- + + ----- do ------------- Medium ---------------- do ------------- Do. 25C ----- Very strong (*) ---- Very strong (*) ---- Very strong (1) ---- Very strong (1). 26 -------+ + + None -------------- None -------------- None -------------- None. 27 -------+ + + ----- do ------------------ do ------------------ do ------------- Do. 28 ------- + + Very light --------- Light ------------- Very light --------- Do. 29 ------- + + None ------------------- do ------------------ do ------------- Do. 30c----- + + ----- do ------------------ do ------------------ do ------------- Do. 31C ----- - Very strong (1) ---- Very strong (1) ---- Very strong (*) ---- Very strong I C =Comparison example. TABLE III Surface Resistance (mf2)-45-50% Relativo Atmospheric IE[umidity Example I I hour After 24 hours 8 days 30 I ----------------- 9XlO5--2XlOB 8XIOr,-2XlO6 6-7XI05 2 ----------------- 1-3xlo6 7-9XI05 4-7XI05 3 ----------------- 4--6XlOB 8-9xlo5 3-7XI05 4 ----------------- 7-SX105 7--OX104 2-4XIO' 6 ----------------- 1-2XIOB 5-7XlO5 ixiob 6 ----------------- 7-SX106 3-4XIOD 5- 7XJ05 3r 7 ----------------- 3-4XI06 4-7XI05 9XI04- 2XlO5 8 ----------------- 8--OX10' 7-8XJ03 2-4XI03 9 ----------------- 6-9xlo5 8-9Xlo4 3-5Xlo4 10 ---------------- 1-3xlos 2-3XIO' 6-gXI03 11 ---------------- 9Xlb4-2XlO5 9XI03-2XIO' r@7XlO3 12 ---------------- 6-9xlo5 7-9XI04 4@5XI04 130 -------------- > 107 7XIO-5XlO5 2-3XlOi 14C -------------- > 107 >107 2- 6XIOG 40 15C -------------- >107 >107 9xlo5-5xlo6 16C -------------- >107 > 107 4--9XlO4 17C -------------- > 107 7XlO-5XlO5 1-2XlO4 18C -------------- >107 6XIO-2XlO5 S-gxloa 19C -------------- > 107 >107 >107 20 ---------------- 2-3XlO5 8-9xloi 3-6xloi 2 1 ---------------- 9XJ04-IXJOS 1-3XlOi 5- 7XlO3 45 22 ---------------- 6-7XI05 4XlO4-lXI06 2--3XlO4 23 ---------------- 7-UX105 2-3XI05 4-5XJ04 24C -------------- > 107 ?-3xlo5 3-4XI04 25C -------------- >107 >107 > 107 26 ---------------- 2-3XIOB 5-8XIO' 1-2XJ04 27 --- ------------ 1-2XlO5 1-5xlo4 gXlo-IXI04 28 ---------------- 8--gXI05 2-5XIO@ 8-gXJ04 29 ---------------- 5-6XI05 9Xlo4-3XI05 6- 7XlO4 50 300 -------------- > 107 7-gXJ04 1-3XI04 31C -------------- > 107 > 107 > 107 I C--Comparative example. TABLEIV Summary evaluation of the antistatic 55 effectiveness afterNumber I I hour 24 hours 8 days 1 ---------------- Mediuni ----------- Good ------------- Good. --------------------- do ------------------ do ------------- Do. --------------------- do ------------------ do ------------- Do. 4---------------- Good/medium ---------- do ------------- Very good. 60 ---------------- Medium ---------------- do ------------- Good. 6 --------------------- do ------------- Medium ----------- Do' 7 --------------------- do -------- ----- Good -------------- Do. 8 ---------------- Good -------------- Very good --------- Very good. 9---------------- Good/medium ---------- do ------------- Do. 10 --------------- Good ------------------- do------------- Do 11 -------------------- do ------------------ do ------------- Do: 65 12 --------------- Good/inedium ----- Good -------------- Do. 13C ------------- Medium ---------------- do ------------- Do. 14C ------------- Very bad ---------- Very bad ---------- Medium. 15C ------------------ do ------------------ do ------------- Do. 16C ------------------ do ------------- Bad --------------- Good. 17C ------------- Medium./bad ------ Good ------------- Very good. 18C ------------------ do ------------------ do ------------- Do. ioc ------------- (1) ------------------------------------- 70 20 ---------- ---- Good/medium ----- Good -------------- Very good. 21 --------------- Good -------------- Very good --------- Do. 22 --------------- Medium ----------- Good ------------- Do. 23 -------------------- do. ----------------- do ------------- Do. 24C ------------- Mediunilbad ----------- do ------------- Do. 25C ------------- (2) ------------------------ ------------ Footnotes at eiad of. table. TABLU IV-Conctinued Summary evaluation of the antistatic efcectiveness afterNumber, 1 hour 24 hours 8 days 26 -------------- Good ------------- Very good --------- Very good. 27- do ------------------ do ------------- Do. 28 ------------------ M-e-dium ----------- Good -------------- Good. 29 --------------- Good/medium ---------- do-. ----------- Very good. 30C ------------- Mediuni/bad ----------- do ------------- Do. 31C ------------- (2) ------------------------------------- I C= Comparison example' Without additive, no effect. The antistatic behavior of the filaments and fibers was also tested by the ash dust method and by measuring the surface resistance in accordance with German Industrial Standard DIN 53,482 VDE 0303, Part 3. These tests were conducted on polyolefin strands of 10 g. reeled off from the spinning reels. In the following examples, the disclosed amounts of 1-ethyl-2-undecyltetrahydropyrimidine was, in each case, admixed to 2 kg. of isotactic polypropylene powder having the relative viscosity of 2.0 (c.@0.1 g./100 ml. at 135' C. in decahydronaphthalene), and the thus-obtained powder is g@anulated in an extruder. In the comparative examples, a@ corresponding procedure was carried out with the bishydroxyethyl derivative of lauryloxypropylamine. The thus-obtained granulated material was spun into threads in a melt spinning apparatus at 245-'-)95' C. by melting and extrusion through an eight-hole nozzle (diameter of the holes: 0.25 mm.), which threads were wound onto spools. From the thus-obtained spools, 10gram strands were wound off, and the surface resistance was measured by means of a "Tera" ohmmeter (Kamphausen; electrode gap: I cm.). The attraction of cigarette ash (ash test) was, measured (after a 24-hour storage at 23' C., 60% relative humidity) after rubbing with a cellulose cloth (height: 0.5 cm. above the ash). Polyolefin threads and -fibers which do not contain any antistat exhibit a surface resistance of >107 MO and strongly attract the ash. means no ash attraction. means ash attraction; Examples 32 to 35 In Examples 32-35, the indicated amount of I-ethyl2 -undecyltetrahydropyrimidine (EUT?) is, in each case, admixed to isotactic polypropylene powder having the relative viscosity of 2.0. The powder is then granulated and spun in a melt spinning apparatus.
[5]3)701)765 9 Data of the melt spinning plant: Melting zone: I ------------------------------- C-- 245 2 -@ ---------------------------- 0 C-- 265 3 ------------------------------- C-- 295 Extrusion speed ------------------ m./min-- 16-18 Conveying capacity ---------------- g./min-- 5.8-6.3 Spinning delay ---------------------------- 35-37 Winding speed -------------------- m./min-- 640 The properties of the thus-produced fhaments are set forth below. Tensile Added elongation, amount of Fineness percent EUTP of thread ktensue Surface (percent (titer) strength resista nee Ash by wt.) fdte.-I ' [p/dt...] I [mu] test Example 32--- 0.3 95/8 348 (1.4) 6,104 + Example 33-.. 0.5 96/8 417 (1.2) 3.104 + Example 34-.- I' 0 99/8 421 (1.3) 4.103 + Example 35--- 4.5 97/8 329 (1.0) 3.103 + I dt... means the weight of 10,000 m. fibre in g. P/d,...=poid dt@.. Comparative Examples 36 to 39 In comparative Example 36, isotactic polypropylene (relative viscosity=2.0) is spun without any additive, and in Comparative Examples 37 and 39, the same isotactic polypropylene is mixed with the disclosed amounts of the additive bishydroxyethyl derivative of lauryloxypropylamine (BHLP) and then spun, under otherwise identical conditions. Tensile Added elongation, amount of Fineness percent BHLP of thread ktonsile Surface [Percent (titer) strength resista nce Ash by wt] [dt...] [Pldt@..]) [ME2] test Comp. Ex. 36. 0 95/8 417 (1.6) >10 7 Comp. Ex. 37- 0.5 101/8 408 (1.2) >10 7 Comp. Ex. 38- 1.0 100/8 368 (1.3) 3.10 6 + Comp. Ex. 39- 4.5 99/8 311 (1.0) 7.10 4 + The comparative examples demonstrate that an antistat (BHLP) highly effective for injection-molded articles of polyolefins cannot be economically employed for threads and fibers, since the onset of an antistatic effect can only be detected at a concentration of I.OVO (or higher). In contrast thereto, the antistatic polyolefin threads and fibers of this invention, surprisingly exhibit an improved effect with considerably smaller concentrations of the tetrahydropyrimidines of this invention, e.g., 6-104 Me at 0.3% antistat concentration. The preceding examples can be repeated with similar success by substituting the genericaffy or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples. -From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. 10 What is
