DE1494013A1 - Process for the production of plasticized, antistatic, thermoplastic masses - Google Patents

Description

Process for the production of plasticized, antistatic, thermoplastic Masses The use of plasticizers for thermo-elastic masses, they Cel uloseester, Polymers or mixed polymerizates such as vinyl chloride, vinylidene chloride, etc., is known. The properties of the polymers let @ n sioii du ch type and amount of the added @eiehmacher change. of those primarily odorless, Migration resistance and smooth processability with len polymers are required vird. In addition, white molding compounds should have good mechanical strengths lend and be phydiologically flawless.

The excellent sound insulation properties of the most popular thermoplastics like z0 3. PVC, which by @anche plasticizers, z. 3.

Polye er or alkyl sulfonic acid esters Jej phenols / cresols, were reduced but still za products with a high surface resistance of 1012 - 1014 ohms, are for c iuse areas of application, such as floor coverings, tranoport tapes, Tape guide strips and similar articles undesirable. They lead to otatic recharges, as their fol @@ n z. B. permanent attraction of dust particles that contribute to pollution from surfaces, or more or less strong electrical discharges, to @@@ en would be.

To eliminate this effect, which is perceived as a disturbance, attempts have been made to to prepare the surfaces of the finished article subsequently with suitable means, The antietatic effect that can be achieved is, however, with heavy use of the ¢ egenetandes only short-lived. It has therefore recently gone over to commercial plasticizers wholly or partially through so-called antistatic plasticizers to replace.

Here and primarily glycol or polyglycol esters of fatty acids or of aliphatic dicarboxylic acids to be mentioned. The previously known antistatic However, plasticizers have various disadvantages, so they are with the polymers, and the commercially available plasticizers used are only tolerated to a limited extent tin tend to migrate, and their antistatic effect is low.

It has now been found that polyethers of the general formula 3 R1-O- (CHR2 - CHR3O) x - (CHR4 - CHR5O) y - R6 in the R1 for a preferably substituted one Aryl radical, R2 - R6 stand for hydrogen or alkyl radicals and 1 is an integer von -10 and y are integers from 0-10, in a special manner as plasticizers Suitable for the production of antistatic, thermoplastic compounds.

The compounds used according to the invention are known per se For example, by reacting optionally substituted phenols or naphthols with alkylene oxides, such as So B. ethylene oxide, propylene oxide, butylene oxide or mixtures of these oxides, with the terminal hydroxyl trapped can then be etherified by alkylating agents.

Any phenols and maphthols can be used as phenol components usable. In order to obtain a specific compatibility of the plasticizer with the soft / non-compliant To achieve thermoplastic masses, the phenolic component is used more or less moderately by introducing suitable subatituents that improve compatibility the polymer. Substituents that may be mentioned are alkyl, halogen, alkoxy @ alkylmero pto, alkylamino, dialkylamino, acylamino and car @ alkoxy groups.

Examples of such aromatic compounds are 2,6-diethylphenol, 2,4,6-triethylphenol, diisobutyl-6-chloro-2-methylphenol, diisobutyl-6-chloro-2-methylphenol, 4-dodeoyl-phenol, 4-n-butylamino-phenol, 4-isooctyl-mercapto-phenol. Hexylnaphtol-2, Heptylnaphtol-2.

Examples of the thermoplastic masses are, for. B. Polymers and Copolymers of ethylene and propylene, styrenes or vinyl chloride, vinylidene chloride or of cellulose esters.

The conversion products used according to the invention are used in the Ubliohen Way, meanwhile, they are alone or mixed with each other and / or mixed with other plasticizers in amounts of 1 - 10 parts by weight, preferably 3 - 40 parts by weight the Adds polymers. This addition can be used in the preparation of the mixture, for example on the Walse, the compounds to be used according to the invention are carried out the demands placed on sinen Weiohmacher with anti-static effect are much better than the previously known substances. In addition to an excellent Processability and above all the high compatibility with the polymers, other plasticizers and stabilizers, the excellent migration resistance and the exceptional strength values of those used with the invention Compounds plasticized thermoplastics u call. Compared to commercially available plasticizers it increases the surface resistance by 4, the specific Durohgangawiderstand Only 3 powers of ten more reduced @ t. Look at the physiological harmlessness of the substances mentioned.

The following examples demonstrate the good antistatic properties the polyether compared to other known plasticizers.

Example 1 60 parts by weight of one by polymerisation in emulsion Polyvinyl chloride produced vem K value 70 are each with 40 parts by weight of one of the antistatic plasticizers listed below with the addition of 0t6 s (refer to u on PVC) an organotin compound as a stabilizer on a 1600 C hot roller Mixed for 10 minutes. The rolled sheet is then pressed into foils at 1600 C, from which the desired test specimens are produced.

The electrical values (specific passage @ resistance @ D 'surface resistance Ro) was determined at 220 Q and 55 relative humidity according to VDE 0303/3.

There are added a) reaction product from triisobuty 1-6-chloro-2-methyl aenol with ethylene oxide, which was produced according to the instructions given below. b) Uzsstzun a product of diisobutyl - @ - ohler-2-methylphenol with ethylene oxide, which after which was made below go @@ en Before @@@ rift. dum verifications become folgetde sandelsübllche antistatic we @ ca @@ c @ er @@@ r herangezeg @@@ c) polyglycol ester of Fettshuren @ittlerer Ket @ enlänge, d) @ lsäurepolygly @olester.

As a non-antibiotic softener, for comparison: e) Dioctyl phthalate.

The values are set out in Table 1.

Table 1 Plasticizer # D = a # 10b # om Ro - a # 10b # Remarks a b a b a 1.8 7 5.5 6 b 7t0 7 2.8 7 e 9.0 7 4e7 7 d - - - - immediately moves from e 7.6 10-4.3 10 The compounds according to the invention are prepared as follows; To a) In 898 parts by weight of triisobutyl-6-chloro-2-methylphenol (produced by duroh Al @ ylation of 6-chloro-2-methylg @ enol with triisobutylene) are 40 parts by weight Caustic potash dissolved and the separated water heated in a vacuum. At 120-130 ° C 897 parts by weight of ethylene oxide are now introduced.

The product is then soluble in cold water. (Cloud point 260 C). To remove the catalyst, the ren tion product is used with 1000 parts by volume 15 iger saline solution stirred 3 x at 60 ° C and the salt solution after Abottzen each deducted from below. Dansch heats the uooer dissolved in the reaction product at a vacuum of 10-20 Torr. The dehydration is finished when the reaction mass has reached a temperature of 1200 0.

Mach @iltration of et @ as excreted salt is obtained 1641 Parts by weight of a light brown colored oil which is soluble in cold water.

To b) In 254.5 parts by weight of diisobutyl-6-chloro-2-methylphenol 11.5 facial parts @ t @ kali dissolved and the separated water ia vacuum annealed. At 1200 0 only 508 parts by weight @ thyleno @ yd are introduced. After that is last Product soluble in cold water, (cloud point 280 c).

If the work-up carried out under a), 506 parts by weight are obtained of a thin oil.

Example @ @e 60 parts by weight of one by polymerization in fritilsion produced PVO vol K value 70 are old Se 35 parts by weight of dioctyl phthalate and per S parts by weight of one of the antistatic softeners listed below as described in Example 1, processed and checked. The values are in the table 2 knocked down. is Will sigesstat. a) Product a) from Example 1 Used for comparison the following non-antistatic plasticizer @ b) dioctyl phthalate.

Table 2 Plasticizers #D = a # 10b # om Ro = 1 # 10b # Notes a b a b a 7.0 8 5.3 8 b 7.6 10 4.3 10 Example 3 Each 60 parts by weight of one PVO produced by polymerization in emulsion with a K value of 70 each have a value of 35 Parts by weight of an alkylsulfonic acid ester of phenol / cresol and 5 parts by weight each one of the anti-inflammatory plasticizers listed below as described in Case 1 processed and checked.

The values are set out in Table 3.

It is added a) reaction product of 2,4,6-triethylphenol with 4 moles of ethylene oxide, prepared according to Example 1.

For comparison it is used b) The one used in the example lo Link.

The comparison is e) alkyl sulfonic acid esters as a non-antistatic plasticizer of phenol / cresol.

Table 3 Plasticizers #D = a # 10b # om R0 i a # 10b # Remarks a 6.0 8 1.1 b b 2.0 9 5.3 8 o 5.3 10 4.9 10 Example 4 60 parts by weight each A PVO produced by polymerization in emulsion with a K value of 70 has been used 30 parts by weight of an alkyl sulfonic acid ester of phenol / crosol and 10 each Oo weight parts one of the below mentioned antistatic soft. Makers like in example oil 1 described, processed and checked.

The values are set out in Table 4.

Be zugesotzt @ a) reaction product of isododecylphenol with Ethylene oxide with a cloud point of 10-12 ° C., prepared according to Example 1. b) Product a) from example 1.

Dom compares c) alkyl sulfonic acid esters as a non-antistatic softener of phenol / cresol.

Table 4 Weichmecher #D = a # 10b # om Ro = a # 10b # Comments a b a b a 2.8 8 1.8 8 b 4.4 8 1.8 8 0 5.3 10 4.9 10 Example 5 60 each Parts by weight of a PVC produced by polymerization in suspension with a K value r0 with 30 parts by weight of an alkyl sulfonic acid of phenol / crosol and 10 parts by weight of one of the antistatic softs listed below. some as described in example 1, processed and tested.

The values are set out in Table 5.

Ks are added; a) Product a) from Example 1.

For comparison, b) Product d) from Example 1 o) Product o) from example 1.

Comparison d) alkylsulfonic acid esters serves as a non-antistatic plasticizer of phenol / cresol.

Table 5 Plasticizers #D = a # 10b # om Ro = a # 10b # Comments 9 6.1 9 4.2 9 b - - - - migrates strongly c 1.4 10 8.7 9 d 20 11 1.6 10

Claims (1)

patent claim process for the production of plasticized, antistatic, thermoplastic compositions, characterized in that polyethers of the general Formula R1 - O - (CHR2 - CHR3 - O) x - (CHR4 - CHR5 - O) y -R6 in which R1 iUr one preferably substituted aryl radicals, R2 to R6 represent hydrogen or alkyl radicals and in which x are whole numbers from 1 to 10 and y are whole numbers from 0 to 10, all antistatic plasticizers for thermoplastic masses are shipped.